Personal care compositions comprising a zinc containing material in an aqueous surfactant composition

ABSTRACT

Disclosed are compositions comprising an effective amount of a zinc containing material having an aqueous solubility within the composition of less than about 25% by weight at 25° C.; from about 5% to about 50% of a surfactant; and from about 40% to about 95% water; wherein the pH of the composition is greater than about 7. Further disclosed are compositions comprising an effective amount of a zinc containing material having an aqueous solubility within the composition of less than about 25% by weight at 25° C.; from about 5% to about 50% of a surfactant; and from about 0.1% to about 5% of a zinc ionophoric material; from about 40% to about 95% water; and wherein the pH of the composition is greater than about 7.

FIELD

[0001] Certain embodiments of the present invention relate to personalcare compositions and methods of treating microbial and fungalinfections on the skin or scalp. Additionally, certain embodiments ofthe present invention relate to methods for the treatment of dandruffand compositions which provide improved anti-dandruff activity.

BACKGROUND

[0002] Of the trace metals, zinc is the second most abundant metal inthe human body, catalyzing nearly every bio-process directly orindirectly through inclusion in many different metalloenzymes. Thecritical role zinc plays can be discerned from the symptoms of dietarydeficiency, which include dermatitis, anorexia, alopecia and impairedoverall growth. Zinc appears especially important to skin health and hasbeen used (typically in the form of zinc oxide or calamine) for over3000 years to control a variety of skin problems. Recent data morespecifically points to the healing and repairing properties of topicalzinc treatment to damaged skin, often resulting in increased rates ofhealing. There is a growing body of biochemical support for thisphenomenon. Since dandruff has been previously shown to representsignificant damage to scalp skin, topical zinc treatment could aid inthe repair process.

[0003] Inorganic salts, such as zinc oxide, have been employed asbacteriostatic and/or fungistatic compounds in a large variety ofproducts including paints, coatings and antiseptics. However, zinc saltsdo not possess as high of a level of biocidal efficacy as might bedesired for many anti-dandruff and skin care applications.

[0004] While the prior art may have addressed some of the problems ofchivying the use of inorganic salts in a large variety of products, theyhave not addressed the problems to the extent of or in the manner of thepresent invention. Therefore, there is a need for an improved personalcare composition comprising a zinc containing material in an aqueoussurfactant composition.

SUMMARY

[0005] An embodiment of the present invention is directed to acomposition comprising an effective amount of a zinc containing materialhaving an aqueous solubility within the composition of less than about25% by weight at 25° C.; from about 5% to about 50% of a surfactant; andfrom about 40% to about 95% water; wherein the pH of the composition isgreater than about 7.

[0006] An additional embodiment of the present invention is directed toa composition comprising an effective amount of a zinc containingmaterial having an aqueous solubility within the composition of lessthan about 25% by weight at 25° C.; from about 5% to about 50% of asurfactant; and from about 0.1% to about 5% of a zinc ionophoricmaterial; from about 40% to about 95% water; and wherein the pH of thecomposition is greater than about 7.

[0007] These and other features, aspects, and advantages of the presentinvention will become evident to those skilled in the art from a readingof the present disclosure.

BRIEF DESCRIPTION OF THE DRAWINGS

[0008]FIG. 1 is a graph showing the relationship between pH and percent(%) soluble zinc.

DETAILED DESCRIPTION

[0009] While the specification concludes with claims which particularlypoint out and distinctly claim the invention, it is believed the presentinvention will be better understood from the following description.

[0010] It has now surprisingly been found, in accordance with thepresent invention, that anti-dandruff efficacy can be dramaticallyincreased in topical compositions by the use of polyvalent metal saltsof pyrithione, such as zinc pyrithione, in combination with zinccontaining material. Therefore an embodiment of the present inventionprovides topical compositions with improved benefits to the skin andscalp (e.g., improved antidandruff efficacy).

[0011] An embodiment of the present invention provides a stablecomposition for zinc containing material (e.g., zinc oxide) dispersionwhere the zinc containing material resides in a particulate form. It hasbeen shown to be challenging to formulate aqueous systems containing azinc containing material such as zinc oxide, due to their uniquephysical and chemical properties. They have a high density (i.e. 3g/cm3), and needs to be evenly dispersed throughout the product so itwill not aggregate or settle. They also have a very-reactive surfacechemistry as well as the propensity to dissolve in systems with pHvalues below 7.5. This has provided a unique understanding concerningthe need to control proton sources or other reactive/coordinatingspecies (e.g., EDTA, citrate).

[0012] An embodiment of the present invention is directed toward acomposition comprising an effective amount of a zinc containing materialhaving an aqueous solubility within the composition of less than about25% by weight at 25° C.; from about 5% to about 50% of a surfactant; andfrom about 40% to about 95% water; wherein the pH of the composition isgreater than about 7.

[0013] Another embodiment of the present invention is directed toward acomposition comprising an effective amount of a zinc containing materialhaving an aqueous solubility within the composition of less than about25% by weight at 25° C.; from about 5% to about 50% of a surfactant; andfrom about 0.1% to about 5% of a zinc ionophoric material; from about40% to about 95% water; and wherein the pH of the composition is greaterthan about 7.

[0014] An embodiment of the present invention is directed toward acomposition comprising labile zinc maintained by choice of an effectivezinc containing material or formation of an effective zinc containingmaterial in situ.

[0015] An embodiment of the present invention provides topical skinand/or hair compositions which provide superior benefits from zincoxide. An embodiment of the present invention also provides a method forcleansing the hair and/or skin. These, and other benefits, will becomereadily apparent from the detailed description.

[0016] An embodiment of the present invention provides topical skinand/or hair compositions which provide superior benefits from zinchydroxycarbonate. An embodiment of the present invention also provides amethod for cleansing the hair and/or skin. These, and other benefits,will become readily apparent from the detailed description.

[0017] The present invention can comprise, consist of, or consistessentially of the essential elements and limitations of the inventiondescribed herein, as well any of the additional or optional ingredients,components, or limitations described herein.

[0018] All percentages, parts and ratios are based upon the total weightof the compositions of the present invention, unless otherwisespecified. All such weights as they pertain to listed ingredients arebased on the active level and, therefore, do not include carriers orby-products that may be included in commercially available materials.

[0019] The components and/or steps, including those which may optionallybe added, of the various embodiments of the present invention, aredescribed in detail below.

[0020] All documents cited are, in relevant part, incorporated herein byreference; the citation of any document is not to be construed as anadmission that it is prior art with respect to the present invention.

[0021] All ratios are weight ratios unless specifically statedotherwise.

[0022] All temperatures are in degrees Celsius, unless specificallystated otherwise.

[0023] Except as otherwise noted, all amounts including quantities,percentages, portions, and proportions, are understood to be modified bythe word “about”, and amounts are not intended to indicate significantdigits.

[0024] Except as otherwise noted, the articles “a”, “an”, and “the” mean“one or more”

[0025] Herein, “comprising” means that other steps and other ingredientswhich do not affect the end result can be added. This term encompassesthe terms “consisting of” and “consisting essentially of”. Thecompositions and methods/processes of the present invention cancomprise, consist of, and consist essentially of the essential elementsand limitations of the invention described herein, as well as any of theadditional or optional ingredients, components, steps, or limitationsdescribed herein.

[0026] Herein, “effective” means an amount of a subject active highenough to provide a significant positive modification of the conditionto be treated. An effective amount of the subject active will vary withthe particular condition being treated, the severity of the condition,the duration of the treatment, the nature of concurrent treatment, andlike factors.

[0027] A. Zinc Containing Material

[0028] The composition of the present invention includes an effectiveamount of a zinc containing material. Herein “zinc containing material”or ZCM means a material comprising zinc bound covalently, and/orionically, or physically by a host material.

[0029] Preferred embodiments of the present invention include aneffective amount of a zinc containing material having an aqueoussolubility within the composition of less than about 25%, by weight, at25° C., more preferably less than about 20%; more preferably less thanabout 15%.

[0030] Preferred embodiments of the present invention include from0.001% to 10% of a zinc containing material; more preferably from 0.01%to 5%; more preferably still from 0.1% to 3%.

[0031] In a preferred embodiment, the zinc containing material has anaverage particle size of from 100 nm to 30 μm.

[0032] Examples of zinc containing materials useful in certainembodiments of the present invention include the following:

[0033] Inorganic Materials: Zinc aluminate, Zinc carbonate, Zinc oxideand materials containing zinc oxide (i.e., calamine), Zinc phosphates(i.e., orthophosphate and pyrophosphate), Zinc selenide, Zinc sulfide,Zinc silicates (i.e., ortho- and meta-zinc silicates), Zincsilicofluoride, Zinc Borate, Zinc hydroxide and hydroxy sulfate,zinc-containing layered materials and combinations thereof.

[0034] Further, layered structures are those with crystal growthprimarily occurring in two dimensions. It is conventional to describelayer structures as not only those in which all the atoms areincorporated in well-defined layers, but also those in which there areions or molecules between the layers, called gallery ions (A. F. Wells“Structural Inorganic Chemistry” Clarendon Press, 1975). Zinc-containinglayered materials (ZLM's) may have zinc incorporated in the layersand/or as more labile components of the gallery ions.

[0035] Many ZLM's occur naturally as minerals. Common examples includehydrozincite (zinc carbonate hydroxide), basic zinc carbonate,aurichalcite (zinc copper carbonate hydroxide), rosasite (copper zinccarbonate hydroxide) and many related minerals that are zinc-containing.Natural ZLM's can also occur wherein anionic layer species such asclay-type minerals (e.g., phyllosilicates) contain ion-exchanged zincgallery ions. All of these natural materials can also be obtainedsynthetically or formed in situ in a composition or during a productionprocess.

[0036] Another common class of ZLM's, which are often, but not always,synthetic, is layered doubly hydroxides, which are generally representedby the formula [M²⁺ _(1−x)M³⁺ _(x)(OH)₂]_(x+)A^(m−) _(x/m).nH₂O and someor all of the divalent ions (M²⁺) would be represented as zinc ions(Crepaldi, E L, Pava, P C, Tronto, J, Valim, J B J. Colloid Interfac.Sci. 2002, 248, 429-42).

[0037] Yet another class of ZLM's can be prepared called hydroxy doublesalts (Morioka, H., Tagaya, H., Karasu, M, Kadokawa, J, Chiba, K Inorg.Chem. 1999, 38, 4211-6). Hydroxy double salts can be represented by thegeneral formula [M²⁺ _(1−x)M²⁺ _(1+x)(OH)_(3(1−y))]⁺A^(n−)_((1=3y)/n).nH₂O where the two metal ion may be different; if they arethe same and represented by zinc, the formula simplifies to[Zn_(1+x)(OH)₂]^(2x+)2xA⁻.nH₂O. This latter formula represents (wherex=0.4) common materials such as zinc hydroxychloride and zinchydroxynitrate. These are related to hydrozincite as well wherein thedivalent anion is replaced by a monovalent anion. These materials canalso be formed in situ in a composition or in or during a productionprocess.

[0038] These classes of ZLM's represent relatively common examples ofthe general category and are not intended to be limiting as to thebroader scope of materials which fit this definition.

[0039] Natural Zinc containing materials/Ores and Minerals: Sphalerite(zinc blende), Wurtzite, Smithsonite, Franklinite, Zincite, Willemite,Troostite, Hemimorphite and combinations thereof.

[0040] Organic Salts: Zinc fatty acid salts (i.e., caproate, laurate,oleate, stearate, etc.), Zinc salts of alkyl sulfonic acids, Zincnaphthenate, Zinc tartrate, Zinc tannate, Zinc phytate, Zincmonoglycerolate, Zinc allantoinate, Zinc urate, Zinc amino acid salts(i.e., methionate, phenylalinate, tryptophanate, cysteinate, etc) andcombinations thereof.

[0041] Polymeric Salts: Zinc polycarboxylates (i.e., polyacrylate), Zincpolysulfate and combinations thereof.

[0042] Physically Adsorbed Forms: Zinc-loaded ion exchange resins, Zincadsorbed on particle surfaces, Composite particles in which zinc saltsare incorporated, (i.e., as core/shell or aggregate morphologies) andcombinations thereof.

[0043] Zinc Salts: zinc oxalate, zinc tannate, zinc tartrate, zinccitrate, zinc oxide, zinc carbonate, zinc hydroxide, zinc oleate, zincphosphate, zinc silicate, zinc stearate, zinc sulfide, zinc undecylate,and the like, and mixtures thereof; preferably zinc oxide or zinccarbonate basic.

[0044] Commercially available sources of zinc oxide include Z-Cote andZ-Cote HPI (BASF), and USP I and USP II (Zinc Corporation of America).

[0045] Commercially available sources of zinc carbonate include ZincCarbonate Basic (Cater Chemicals: Bensenville, Ill., USA), ZincCarbonate (Shepherd Chemicals: Norwood, Ohio, USA), Zinc Carbonate (CPSUnion Corp.: New York, N.Y., USA), Zinc Carbonate (Elementis Pigments:Durham, UK), and Zinc Carbonate AC (Bruggemann Chemical: Newtown Square,Pa., USA).

[0046] Zinc Salts That Become Insoluble Above a pH of 7: zinc acetate,zinc chloride, zinc bromide, zinc fluoride, zinc iodide, zinc sulfate,zinc citrate, zinc lactate, zinc nitrate, zinc propionate, zincsalicylate, zinc tartrate, zinc valerate, zinc gluconate, zinc selenate,zinc benzoate, zinc borate, zinc bromate, zinc formate, zincglycerophosphate, zinc picrate, zinc butyrate, and the like, andcombinations thereof.

[0047] Definition of ZCM Solubility: A zinc containing material with asolubility of less than 25% will have a measurable % soluble zinc valuebelow a threshold value determined by the weight percent and molecularweight of the zinc compound. The theoretical threshold value can becalculated by the following equation (see examples in the Table): 0.25 *wt. % Zn Compoundin Composition * moles of Zinc in Compound * 65.39 (MWof Zn) MW of Zn Compound % soluble Zn⁺²; (if 25 wt. % of % Zn Compoundzinc source is Zinc Compound Formula in Composition soluble)* Zinc OxideZnO 1.0%  0.20% Zinc Carbonate Zn₅(CO₃)₂(OH)₆ 1.0%  0.15% Basic(Hydrozincite) Zinc Stearate Zn(C₁₈H₃₅O₂)₂ 1.0% 0.026%

[0048] B. Zinc Ionophoric Material (ZIM)

[0049] In another embodiment of the present invention, the compositionfurther includes a zinc ionophoric material. Herein, “zinc ionophoricmaterial” and “ZIM” means a material which is or forms a hydrophobicmolecule capable of increasing cell permeability to zinc ions (i.e.,exhibiting zinc ionophoric behavior). Without being bound by theory, itis believed that ZIMs shield the charge of the zinc ion to betransported, enabling it to penetrate the hydrophobic interior of thelipid bilayer. ZIMs may be channel-forming ionophores or mobile ioncarriers. ZIMs may be those commonly known as zinc ionophores or thosethat are hydrophobic zinc chelators that possess zinc ionophoricbehavior. Hydrophobic zinc chelators are materials that bind zinc andincrease hydrophobicity of zinc ions such that, for example, it willpartition into non-aqueous solvents. ZIMs can be effective includingzinc being present in the composition or zinc being available within thesystem wherein a ZIM is present, yet preferred ZIMs contain zinc ions;i.e, zinc salt forms of materials exhibiting zinc ionophoric behavior.

[0050] Preferred embodiments include from 0.01% to 5% of a ZIM; morepreferably from 0.1% to 2%.

[0051] In embodiments having a zinc containing material and a ZIM, theratio of zinc containing material to ZIM is preferably from 5:100 to5:1; more preferably from about 2:10 to 3:1; more preferably still from1:2 to 2:1.

[0052] In preferred embodiments of the present invention, the ZIM has apotency against target microorganisms such that the minimum inhibitoryconcentration (“MIC”) is below 5000 parts per million. The MIC is ameasurement well understood by those skilled in the art and isindicative of anti-fungal efficacy. Generally, the lower the value ofthe composition, the better its anti-fungal efficacy, due to increasedinherent ability of the anti-dandruff agent to inhibit the growth ofmicroorganisms. The lowest tested dilution of anti-microbial active thatyields no growth is defined as the MIC.

[0053] Examples of ZIMs useful in embodiments of the present inventioninclude the following: Class Name (Synonyms) Structure Bio-molecules,Peptides and Naturally Occurring Materials and derivatives thereofhaving zinc ionophoric behavior Lasalocid (X537A)

A23187 (Calcimycin)

4-Br A23187

Ionomycin

Cyclosporin A Cyclic undecapeptide: cyclo-(MeBMT-Abu-Sar-MeLeu-Val-MeLeu-Ala-D-Ala-MeLeu- MeLeu-MeVal) HydroxyquinolinesDiodoquin (Iodoquinol; 5,7- Diodo-8- hydroxyquinoline)

Enterovioform (Iodochloro hydroxyquinoline; 5-Cl, 7-I- 8-hydroxyquinoline)

Sterosan (Chloroquinaldol; 2- Me, 5,7-Dichloro-8- hydroxyquinoline)

5-7-Bibromo-8- hydroxyquinoline

Sulfur-Based Compounds Tetra-n-butyl thiuram Disulfide (TBTDS)

Transport Albumin, histidine, Enhancers arachidonic acid, picolinicacid, dihydroxyvitamin D₃, ethylmaltol

[0054] In a preferred embodiment, the ZIM is pyrithione or a polyvalentmetal salt of pyrithione. Any form of polyvalent metal pyrithione saltsmay be used, including platelet and needle structures. Preferred saltsfor use herein include those formed from the polyvalent metalsmagnesium, barium, bismuth, strontium, copper, zinc, cadmium, zirconiumand mixtures thereof, more preferably zinc. Even more preferred for useherein is the zinc salt of 1-hydroxy-2-pyridinethione (known as “zincpyrithione” or “ZPT”); more preferably ZPT in platelet particle form,wherein the particles have an average size of up to about 20 μm,preferably up to about 5 μm, more preferably up to about 2.5 μm.

[0055] Pyridinethione anti-microbial and anti-dandruff agents aredescribed, for example, in U.S. Pat. No. 2,809,971; U.S. Pat. No.3,236,733; U.S. Pat. No. 3,753,196; U.S. Pat. No. 3,761,418; U.S. Pat.No. 4,345,080; U.S. Pat. No. 4,323,683; U.S. Pat. No. 4,379,753; andU.S. Pat. No. 4,470,982.

[0056] It is further contemplated that when ZPT is used as theanti-microbial particulate in the anti-microbial compositions herein,that an additional benefit of hair growth or re-growth may be stimulatedor regulated, or both, or that hair loss may be reduced or inhibited, orthat hair may appear thicker or fuller.

[0057] Zinc pyrithione may be made by reacting1-hydroxy-2-pyridinethione (i.e., pyrithione acid) or a soluble saltthereof with a zinc salt (e.g. zinc sulfate) to form a zinc pyrithioneprecipitate, as illustrated in U.S. Pat. No. 2,809,971.

[0058] C. Topical Carrier

[0059] In a preferred embodiment, the composition of the presentinvention is in the form of a topical compositions, which includes atopical carrier. Preferably, the topical carrier is selected from abroad range of traditional personal care carriers depending on the typeof composition to be formed. By suitable selections of compatiblecarriers, it is contemplated that such a composition is prepared in theform of daily skin or hair products including conditioning treatments,cleansing products, such as hair and/or scalp shampoos, body washes,hand cleansers, water-less hand sanitizer/cleansers, facial cleansersand the like.

[0060] In a preferred embodiment, the carrier is water. Preferably thecompositions of the present invention comprise from 40% to 95% water byweight of the composition; preferably from 50% to 85%, more preferablystill from 60% to 80%.

[0061] D. Detersive Surfactant

[0062] The composition of the present invention includes a detersivesurfactant. The detersive surfactant component is included to providecleaning performance to the composition. The detersive surfactantcomponent in turn comprises anionic detersive surfactant, zwitterionicor amphoteric detersive surfactant, or a combination thereof. Suchsurfactants should be physically and chemically compatible with theessential components described herein, or should not otherwise undulyimpair product stability, aesthetics or performance.

[0063] Suitable anionic detersive surfactant components for use in thecomposition herein include those which are known for use in hair care orother personal care cleansing compositions. The concentration of theanionic surfactant component in the composition should be sufficient toprovide the desired cleaning and lather performance, and generally rangefrom about 5% to about 50%, preferably from about 8% to about 30%, morepreferably from about 10% to about 25%, even more preferably from about12% to about 22%.

[0064] Preferred anionic surfactants suitable for use in thecompositions are the alkyl and alkyl ether sulfates. These materialshave the respective formulae ROSO₃M and RO(C₂H₄O)_(x)SO₃M, wherein R isalkyl or alkenyl of from about 8 to about 18 carbon atoms, x is aninteger having a value of from 1 to 10, and M is a cation such asammonium, alkanolamines, such as triethanolamine, monovalent metals,such as sodium and potassium, and polyvalent metal cations, such asmagnesium, and calcium.

[0065] Preferably, R has from about 8 to about 18 carbon atoms, morepreferably from about 10 to about 16 carbon atoms, even more preferablyfrom about 12 to about 14 carbon atoms, in both the alkyl and alkylether sulfates. The alkyl ether sulfates are typically made ascondensation products of ethylene oxide and monohydric alcohols havingfrom about 8 to about 24 carbon atoms. The alcohols can be synthetic orthey can be derived from fats, e.g., coconut oil, palm kernel oil,tallow. Lauryl alcohol and straight chain alcohols derived from coconutoil or palm kernel oil are preferred. Such alcohols are reacted withbetween about 0 and about 10, preferably from about 2 to about 5, morepreferably about 3, molar proportions of ethylene oxide, and theresulting mixture of molecular species having, for example, an averageof 3 moles of ethylene oxide per mole of alcohol, is sulfated andneutralized.

[0066] Other suitable anionic detersive surfactants are thewater-soluble salts of organic, sulfuric acid reaction productsconforming to the formula [R¹—SO₃-M] where R¹ is a straight or branchedchain, saturated, aliphatic hydrocarbon radical having from about 8 toabout 24, preferably about 10 to about 18, carbon atoms; and M is acation described hereinbefore.

[0067] Still other suitable anionic detersive surfactants are thereaction products of fatty acids esterified with isethionic acid andneutralized with sodium hydroxide where, for example, the fatty acidsare derived from coconut oil or palm kernel oil; sodium or potassiumsalts of fatty acid amides of methyl tauride in which the fatty acids,for example, are derived from coconut oil or palm kernel oil. Othersimilar anionic surfactants are described in U.S. Pat. Nos. 2,486,921;2,486,922; and 2,396,278.

[0068] Other anionic detersive surfactants suitable for use in thecompositions are the succinnates, examples of which include disodiumN-octadecylsulfosuccinnate; disodium lauryl sulfosuccinate; diammoniumlauryl sulfosuccinate; tetrasodiumN-(1,2-dicarboxyethyl)-N-octadecylsulfosuccinnate; diamyl ester ofsodium sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid;and dioctyl esters of sodium sulfosuccinic acid.

[0069] Other suitable anionic detersive surfactants include olefinsulfonates having about 10 to about 24 carbon atoms. In addition to thetrue alkene sulfonates and a proportion of hydroxy-alkanesulfonates, theolefin sulfonates can contain minor amounts of other materials, such asalkene disulfonates depending upon the reaction conditions, proportionof reactants, the nature of the starting olefins and impurities in theolefin stock and side reactions during the sulfonation process. A nonlimiting example of such an alpha-olefin sulfonate mixture is describedin U.S. Pat. No. 3,332,880.

[0070] Another class of anionic detersive surfactants suitable for usein the compositions are the beta-alkyloxy alkane sulfonates. Thesesurfactants conform to the formula

[0071] where R¹ is a straight chain alkyl group having from about 6 toabout 20 carbon atoms, R² is a lower alkyl group having from about 1 toabout 3 carbon atoms, preferably 1 carbon atom, and M is a water-solublecation as described hereinbefore.

[0072] Preferred anionic detersive surfactants for use in thecompositions include sodium lauryl sulfate, sodium laureth sulfate,triethylamine lauryl sulfate, triethylamine laureth sulfate,triethanolamine lauryl sulfate, triethanolamine laureth sulfate,monoethanolamine lauryl sulfate, monoethanolamine laureth sulfate,diethanolamine lauryl sulfate, diethanolamine laureth sulfate, ammoniumlauryl sulfate, ammonium laureth sulfate, lauric monoglyceride sodiumsulfate, potassium lauryl sulfate, potassium laureth sulfate, sodiumlauryl sarcosinate, sodium lauroyl sarcosinate, lauryl sarcosine, cocoylsarcosine, ammonium cocoyl sulfate, ammonium lauroyl sulfate, sodiumcocoyl sulfate, sodium lauroyl sulfate, potassium cocoyl sulfate,potassium lauryl sulfate, monoethanolamine cocoyl sulfate,monoethanolamine lauryl sulfate, sodium tridecyl benzene sulfonate,sodium dodecyl benzene sulfonate, sodium cocoyl isethionate, andcombinations thereof. Most preferred anionic detersive surfactantsinclude sodium lauryl sulfate and sodium laureth sulfate.

[0073] Suitable amphoteric or zwitterionic detersive surfactants for usein the composition herein include those which are known for use in haircare or other personal care cleansing. Concentration of such amphotericdetersive surfactants preferably ranges from about 0.5% to about 20%,preferably from about 1% to about 10%. Non limiting examples of suitablezwitterionic or amphoteric surfactants are described in U.S. Pat. No.5,104,646 (Bolich Jr. et al.), U.S. Pat. No. 5,106,609 (Bolich Jr. etal.).

[0074] Amphoteric detersive surfactants suitable for use in thecomposition are well known in the art, and include those surfactantsbroadly described as derivatives of aliphatic secondary and tertiaryamines in which the aliphatic radical can be straight or branched chainand wherein one of the aliphatic substituents contains from about 8 toabout 18 carbon atoms and one contains an anionic group such as carboxy,sulfonate, sulfate, phosphate, or phosphonate. Preferred amphotericdetersive surfactants for use in the present invention includecocoamphoacetate, cocoamphodiacetate, lauroamphoacetate,lauroamphodiacetate, and mixtures thereof.

[0075] Zwitterionic detersive surfactants suitable for use in thecomposition are well known in the art, and include those surfactantsbroadly described as derivatives of aliphatic quaternary ammonium,phosphonium, and sulfonium compounds, in which the aliphatic radicalscan be straight or branched chain, and wherein one of the aliphaticsubstituents contains from about 8 to about 18 carbon atoms and onecontains an anionic group such as carboxy, sulfonate, sulfate, phosphateor phosphonate. Zwitterionics such as betaines are preferred.

[0076] The compositions of the present invention may further compriseadditional surfactants for use in combination with the anionic detersivesurfactant component described hereinbefore. Suitable optionalsurfactants include nonionic and cationic surfactants. Any suchsurfactant known in the art for use in hair or personal care productsmay be used, provided that the optional additional surfactant is alsochemically and physically compatible with the essential components ofthe composition, or does not otherwise unduly impair productperformance, aesthetics or stability. The concentration of the optionaladditional surfactants in the composition may vary with the cleansing orlather performance desired, the optional surfactant selected, thedesired product concentration, the presence of other components in thecomposition, and other factors well known in the art.

[0077] Non limiting examples of other anionic, zwitterionic, amphotericor optional additional surfactants suitable for use in the compositionsare described in McCutcheon's, Emulsifiers and Detergents, 2002 Annual,published by M. C. Publishing Co., and U.S. Pat. Nos. 3,929,678,2,658,072; 2,438,091; 2,528,378.

[0078] E. Dispersed Particles

[0079] The composition of the present invention may include dispersedparticles. In the compositions of the present invention, it ispreferable to incorporate at least 0.025% by weight of the dispersedparticles, more preferably at least 0.05%, still more preferably atleast 0.1%, even more preferably at least 0.25%, and yet more preferablyat least 0.5% by weight of the dispersed particles. In the compositionsof the present invention, it is preferable to incorporate no more thanabout 20% by weight of the dispersed particles, more preferably no morethan about 10%, still more preferably no more than 5%, even morepreferably no more than 3%, and yet more preferably no more than 2% byweight of the dispersed particles.

[0080] F. Aqueous Carrier

[0081] The compositions of the present invention are typically in theform of pourable liquids (under ambient conditions). The compositionswill therefore typically comprise an aqueous carrier, which is presentat a level of from about 20% to about 95%, preferably from about 60% toabout 85%. The aqueous carrier may comprise water, or a miscible mixtureof water and organic solvent, but preferably comprises water withminimal or no significant concentrations of organic solvent, except asotherwise incidentally incorporated into the composition as minoringredients of other essential or optional components.

[0082] G. Additional Components

[0083] The compositions of the present invention may further compriseone or more optional components known for use in hair care or personalcare products, provided that the optional components are physically andchemically compatible with the essential components described herein, ordo not otherwise unduly impair product stability, aesthetics orperformance. Individual concentrations of such optional components mayrange from about 0.001% to about 10%.

[0084] Non-limiting examples of optional components for use in thecomposition include cationic polymers, conditioning agents (hydrocarbonoils, fatty esters, silicones), anti dandruff agents, suspending agents,viscosity modifiers, dyes, nonvolatile solvents or diluents (watersoluble and insoluble), pearlescent aids, foam boosters, additionalsurfactants or nonionic cosurfactants, pediculocides, pH adjustingagents, perfumes, preservatives, chelants, proteins, skin active agents,sunscreens, UV absorbers, vitamins, minerals, herbal/fruit/foodextracts, sphingolipids derivatives or synthetical derivative, and clay.

[0085] 1. Cationic Polymers

[0086] The compositions of the present invention may contain a cationicpolymer. Concentrations of the cationic polymer in the compositiontypically range from about 0.05% to about 3%, preferably from about0.075% to about 2.0%, more preferably from about 0.1% to about 1.0%.Preferred cationic polymers will have cationic charge densities of atleast about 0.9 meq/gm, preferably at least about 1.2 meq/gm, morepreferably at least about 1.5 meq/gm, but also preferably less thanabout 7 meq/gm, more preferably less than about 5 meq/gm, at the pH ofintended use of the composition, which pH will generally range fromabout pH 3 to about pH 9, preferably between about pH 4 and about pH 8.Herein, “cationic charge density” of a polymer refers to the ratio ofthe number of positive charges on the polymer to the molecular weight ofthe polymer. The average molecular weight of such suitable cationicpolymers will generally be between about 10,000 and 10 million,preferably between about 50,000 and about 5 million, more preferablybetween about 100,000 and about 3 million.

[0087] Suitable cationic polymers for use in the compositions of thepresent invention contain cationic nitrogen-containing moieties such asquaternary ammonium or cationic protonated amino moieties. The cationicprotonated amines can be primary, secondary, or tertiary amines(preferably secondary or tertiary), depending upon the particularspecies and the selected pH of the composition. Any anionic counterionscan be used in association with the cationic polymers so long as thepolymers remain soluble in water, in the composition, or in a coacervatephase of the composition, and so long as the counterions are physicallyand chemically compatible with the essential components of thecomposition or do not otherwise unduly impair product performance,stability or aesthetics. Non limiting examples of such counterionsinclude halides (e.g., chloride, fluoride, bromide, iodide), sulfate andmethylsulfate.

[0088] Non limiting examples of such polymers are described in the CTFACosmetic Ingredient Dictionary, 3rd edition, edited by Estrin, Crosley,and Haynes, (The Cosmetic, Toiletry, and Fragrance Association, Inc.,Washington, D.C. (1982)).

[0089] Non limiting examples of suitable cationic polymers includecopolymers of vinyl monomers having cationic protonated amine orquaternary ammonium functionalities with water soluble spacer monomerssuch as acrylamide, methacrylamide, alkyl and dialkyl acrylamides, alkyland dialkyl methacrylamides, alkyl acrylate, alkyl methacrylate, vinylcaprolactone or vinyl pyrrolidone.

[0090] Suitable cationic protonated amino and quaternary ammoniummonomers, for inclusion in the cationic polymers of the compositionherein, include vinyl compounds substituted with dialkylaminoalkylacrylate, dialkylaminoalkyl methacrylate, monoalkylaminoalkyl acrylate,monoalkylaminoalkyl methacrylate, trialkyl methacryloxyalkyl ammoniumsalt, trialkyl acryloxyalkyl ammonium salt, diallyl quaternary ammoniumsalts, and vinyl quaternary ammonium monomers having cyclic cationicnitrogen-containing rings such as pyridinium, imidazolium, andquaternized pyrrolidone, e.g., alkyl vinylimidazolium, alkyl vinylpyridinium, alkyl vinyl pyrrolidone salts.

[0091] Other suitable cationic polymers for use in the compositionsinclude copolymers of 1-vinyl-2-pyrrolidone and1-vinyl-3-methylimidazolium salt (e.g., chloride salt) (referred to inthe industry by the Cosmetic, Toiletry, and Fragrance Association,“CTFA”, as Polyquaternium-16); copolymers of 1-vinyl-2-pyrrolidone anddimethylaminoethyl methacrylate (referred to in the industry by CTFA asPolyquaternium-11); cationic diallyl quaternary ammonium-containingpolymers, including, for example, dimethyldiallylammonium chloridehomopolymer, copolymers of acrylamide and dimethyldiallylammoniumchloride (referred to in the industry by CTFA as Polyquaternium 6 andPolyquaternium 7, respectively); amphoteric copolymers of acrylic acidincluding copolymers of acrylic acid and dimethyldiallylammoniumchloride (referred to in the industry by CTFA as Polyquaternium 22),terpolymers of acrylic acid with dimethyldiallylammonium chloride andacrylamide (referred to in the industry by CTFA as Polyquaternium 39),and terpolymers of acrylic acid with methacrylamidopropyltrimethylammonium chloride and methylacrylate (referred to in theindustry by CTFA as Polyquaternium 47). Preferred cationic substitutedmonomers are the cationic substituted dialkylaminoalkyl acrylamides,dialkylaminoalkyl methacrylamides, and combinations thereof. Thesepreferred monomers conform the to the formula

[0092] wherein R¹ is hydrogen, methyl or ethyl; each of R², R³ and R⁴are independently hydrogen or a short chain alkyl having from about 1 toabout 8 carbon atoms, preferably from about 1 to about 5 carbon atoms,more preferably from about 1 to about 2 carbon atoms; n is an integerhaving a value of from about 1 to about 8, preferably from about 1 toabout 4; and X is a counterion. The nitrogen attached to R², R³ and R⁴may be a protonated amine (primary, secondary or tertiary), but ispreferably a quaternary ammonium wherein each of R², R³ and R⁴ are alkylgroups a non limiting example of which is polymethyacrylamidopropyltrimonium chloride, available under the trade name Polycare 133, fromRhone-Poulenc, Cranberry, N.J., U.S.A.

[0093] Other suitable cationic polymers for use in the compositioninclude polysaccharide polymers, such as cationic cellulose derivativesand cationic starch derivatives. Suitable cationic polysaccharidepolymers include those which conform to the formula

[0094] wherein A is an anhydroglucose residual group, such as a starchor cellulose anhydroglucose residual; R is an alkylene oxyalkylene,polyoxyalkylene, or hydroxyalkylene group, or combination thereof; R1,R2, and R3 independently are alkyl, aryl, alkylaryl, arylalkyl,alkoxyalkyl, or alkoxyaryl groups, each group containing up to about 18carbon atoms, and the total number of carbon atoms for each cationicmoiety (i.e., the sum of carbon atoms in R1, R2 and R3) preferably beingabout 20 or less; and X is an anionic counterion as described inhereinbefore.

[0095] Preferred cationic cellulose polymers are salts of hydroxyethylcellulose reacted with trimethyl ammonium substituted epoxide, referredto in the industry (CTFA) as Polyquaternium 10 and available fromAmerchol Corp. (Edison, N.J., USA) in their Polymer LR, JR, and KGseries of polymers. Other suitable types of cationic cellulose includesthe polymeric quaternary ammonium salts of hydroxyethyl cellulosereacted with lauryl dimethyl ammonium-substituted epoxide referred to inthe industry (CTFA) as Polyquaternium 24. These materials are availablefrom Amerchol Corp. under the tradename Polymer LM-200.

[0096] Other suitable cationic polymers include cationic guar gumderivatives, such as guar hydroxypropyltrimonium chloride, specificexamples of which include the Jaguar series commercially avaialable fromRhone-Poulenc Incorporated and the N-Hance series commercially availablefrom Aqualon Division of Hercules, Inc. Other suitable cationic polymersinclude quaternary nitrogen-containing cellulose ethers, some examplesof which are described in U.S. Pat. No. 3,962,418. Other suitablecationic polymers include copolymers of etherified cellulose, guar andstarch, some examples of which are described in U.S. Pat. No. 3,958,581.When used, the cationic polymers herein are either soluble in thecomposition or are soluble in a complex coacervate phase in thecomposition formed by the cationic polymer and the anionic, amphotericand/or zwitterionic detersive surfactant component describedhereinbefore. Complex coacervates of the cationic polymer can also beformed with other charged materials in the composition.

[0097] Techniques for analysis of formation of complex coacervates areknown in the art. For example, microscopic analyses of the compositions,at any chosen stage of dilution, can be utilized to identify whether acoacervate phase has formed. Such coacervate phase will be identifiableas an additional emulsified phase in the composition. The use of dyescan aid in distinguishing the coacervate phase from other insolublephases dispersed in the composition.

[0098] 2. Nonionic Polymers

[0099] Polyalkylene glycols having a molecular weight of more than about1000 are useful herein. Useful are those having the following generalformula:

[0100] wherein R⁹⁵ is selected from the group consisting of H, methyl,and mixtures thereof. Polyethylene glycol polymers useful herein arePEG-2M (also known as Polyox WSR® N-10, which is available from UnionCarbide and as PEG-2,000); PEG-5M (also known as Polyox WSR® N-35 andPolyox WSR® N-80, available from Union Carbide and as PEG-5,000 andPolyethylene Glycol 300,000); PEG-7M (also known as Polyox WSR® N-750available from Union Carbide); PEG-9M (also known as Polyox WSR® N-3333available from Union Carbide); and PEG-14 M (also known as Polyox WSR®N-3000 available from Union Carbide).

[0101] 3. Conditioning Agents

[0102] Conditioning agents include any material which is used to give aparticular conditioning, benefit to hair and/or skin. In hair treatmentcompositions, suitable conditioning agents are those which deliver oneor more benefits relating to shine, softness, combability, antistaticproperties, wet-handling, damage, manageability, body, and greasiness.The conditioning agents useful in the compositions of the presentinvention typically comprise a water insoluble, water dispersible,non-volatile, liquid that forms emulsified, liquid particles. Suitableconditioning agents for use in the composition are those conditioningagents characterized generally as silicones (e.g., silicone oils,cationic silicones, silicone gums, high refractive silicones, andsilicone resins), organic conditioning oils (e.g., hydrocarbon oils,polyolefins, and fatty esters) or combinations thereof, or thoseconditioning agents which otherwise form liquid, dispersed particles inthe aqueous surfactant matrix herein. Such conditioning agents should bephysically and chemically compatible with the essential components ofthe composition, and should not otherwise unduly impair productstability, aesthetics or performance.

[0103] The concentration of the conditioning agent in the compositionshould be sufficient to provide the desired conditioning benefits, andas will be apparent to one of ordinary skill in the art. Suchconcentration can vary with the conditioning agent, the conditioningperformance desired, the average size of the conditioning agentparticles, the type and concentration of other components, and otherlike factors.

[0104] 1. Silicones

[0105] The conditioning agent of the compositions of the presentinvention is preferably an insoluble silicone conditioning agent. Thesilicone conditioning agent particles may comprise volatile silicone,non-volatile silicone, or combinations thereof. Preferred arenon-volatile silicone conditioning agents. If volatile silicones arepresent, it will typically be incidental to their use as a solvent orcarrier for commercially available forms of non-volatile siliconematerials ingredients, such as silicone gums and resins. The siliconeconditioning agent particles may comprise a silicone fluid conditioningagent and may also comprise other ingredients, such as a silicone resinto improve silicone fluid deposition efficiency or enhance glossiness ofthe hair.

[0106] The concentration of the silicone conditioning agent typicallyranges from about 0.01% to about 10%, preferably from about 0.1% toabout 8%, more preferably from about 0.1% to about 5%, more preferablyfrom about 0.2% to about 3%. Non-limiting examples of suitable siliconeconditioning agents, and optional suspending agents for the silicone,are described in U.S. Reissue Pat. No. 34,584, U.S. Pat. No. 5,104,646,and U.S. Pat. No. 5,106,609. The silicone conditioning agents for use inthe compositions of the present invention preferably have a viscosity,as measured at 25° C., from about 20 to about 2,000,000 centistokes(“csk”), more preferably from about 1,000 to about 1,800,000 csk, evenmore preferably from about 50,000 to about 1,500,000 csk, morepreferably from about 100,000 to about 1,500,000 csk.

[0107] The dispersed silicone conditioning agent particles typicallyhave a number average particle diameter ranging from about 0.01 μm toabout 50 μm. For small particle application to hair, the number averageparticle diameters typically range from about 0.01 μm to about 4 μm,preferably from about 0.01 μm to about 2 μm, more preferably from about0.01 μm to about 0.5 μm. For larger particle application to hair, thenumber average particle diameters typically range from about 4 μm toabout 50 μm, preferably from about 6 μm to about 30 μm, more preferablyfrom about 91 μm to about 20 μm, more preferably from about 12 μm toabout 18 μm.

[0108] Background material on silicones including sections discussingsilicone fluids, gums, and resins, as well as manufacture of silicones,are found in Encyclopedia of Polymer Science and Engineering, vol. 15,2d ed., pp 204-308, John Wiley & Sons, Inc. (1989).

[0109] a. Silicone Oils

[0110] Silicone fluids include silicone oils, which are flowablesilicone materials having a viscosity, as measured at 25° C., less than1,000,000 csk, preferably from about 5 csk to about 1,000,000 csk, morepreferably from about 100 csk to about 600,000 csk. Suitable siliconeoils for use in the compositions of the present invention includepolyalkyl siloxanes, polyaryl siloxanes, polyalkylaryl siloxanes,polyether siloxane copolymers, and mixtures thereof. Other insoluble,non-volatile silicone fluids having hair conditioning properties mayalso be used.

[0111] Silicone oils include polyalkyl or polyaryl siloxanes whichconform to the following Formula (III):

[0112] wherein R is aliphatic, preferably alkyl or alkenyl, or aryl, Rcan be substituted or unsubstituted, and x is an integer from 1 to about8,000. Suitable R groups for use in the compositions of the presentinvention include, but are not limited to: alkoxy, aryloxy, alkaryl,arylalkyl, arylalkenyl, alkamino, and ether-substituted,hydroxyl-substituted, and halogen-substituted aliphatic and aryl groups.Suitable R groups also include cationic amines and quaternary ammoniumgroups.

[0113] Preferred alkyl and alkenyl substituents are C₁ to C₅ alkyls andalkenyls, more preferably from C₁ to C₄, more preferably from C₁ to C₂.The aliphatic portions of other alkyl-, alkenyl-, or alkynyl-containinggroups (such as alkoxy, alkaryl, and alkamino) can be straight orbranched chains, and are preferably from C, to C5, more preferably fromC₁ to C₄, even more preferably from C₁ to C₃, more preferably from C₁ toC₂. As discussed above, the R substituents can also contain aminofunctionalities (e.g. alkamino groups), which can be primary, secondaryor tertiary amines or quaternary ammonium. These include mono-, di- andtri-alkylamino and alkoxyamino groups, wherein the aliphatic portionchain length is preferably as described herein.

[0114] b. Amino and Cationic Silicones

[0115] Cationic silicone fluids suitable for use in the compositions ofthe present invention include, but are not limited to, those whichconform to the general formula (V):

(R₁)_(a)G_(3-a)—Si—(—OSiG₂)_(n)—(—OSiG_(b)(R₁)_(2-b))_(m)—O—SiG_(3-a)(R¹)_(a)

[0116] wherein G is hydrogen, phenyl, hydroxy, or C₁-C₈ alkyl,preferably methyl; a is 0 or an integer having a value from 1 to 3,preferably 0; b is 0 or 1, preferably 1; n is a number from 0 to 1,999,preferably from 49 to 499; m is an integer from 1 to 2,000, preferablyfrom 1 to 10; the sum of n and m is a number from 1 to 2,000, preferablyfrom 50 to 500; R₁ is a monovalent radical conforming to the generalformula CqH_(2q)L, wherein q is an integer having a value from 2 to 8and L is selected from the following groups:

—N(R₂)CH₂—CH₂—N(R₂)₂

—N(R₂)₂

—N(R₂)₃A⁻

—N(R₂)CH₂—CH₂—NR₂H₂A⁻

[0117] wherein R₂ is hydrogen, phenyl, benzyl, or a saturatedhydrocarbon radical, preferably an alkyl radical from about C₁ to aboutC₂₀, and A⁻ is a halide ion.

[0118] An especially preferred cationic silicone corresponding toformula (V) is the polymer known as “trimethylsilylamodimethicone”,which is shown below in formula (VI):

[0119] Other silicone cationic polymers which may be used in thecompositions of the present invention are represented by the generalformula (VII):

[0120] wherein R³ is a monovalent hydrocarbon radical from C₁ to C₁₈,preferably an alkyl or alkenyl radical, such as methyl; R₄ is ahydrocarbon radical, preferably a C₁ to C₁₈ alkylene radical or a C₁₀ toC₁₈ alkyleneoxy radical, more preferably a C₁ to C₈ alkyleneoxy radical;Q⁻ is a halide ion, preferably chloride; r is an average statisticalvalue from 2 to 20, preferably from 2 to 8; s is an average statisticalvalue from 20 to 200, preferably from 20 to 50. A preferred polymer ofthis class is known as UCARE SILICONE ALE 56™, available from UnionCarbide.

[0121] c. Silicone Gums

[0122] Other silicone fluids suitable for use in the compositions of thepresent invention are the insoluble silicone gums. These gums arepolyorganosiloxane materials having a viscosity, as measured at 25° C.,of greater than or equal to 1,000,000 csk. Silicone gums are describedin U.S. Pat. No. 4,152,416; Noll and Walter, Chemistry and Technology ofSilicones, New York: Academic Press (1968); and in General ElectricSilicone Rubber Product Data Sheets SE 30, SE 33, SE 54 and SE 76.Specific non-limiting examples of silicone gums for use in thecompositions of the present invention include polydimethylsiloxane,(polydimethylsiloxane) (methylvinylsiloxane) copolymer,poly(dimethylsiloxane) (diphenyl siloxane)(methylvinylsiloxane)copolymer and mixtures thereof.

[0123] d. High Refractive Index Silicones

[0124] Other non-volatile, insoluble silicone fluid conditioning agentsthat are suitable for use in the compositions of the present inventionare those known as “high refractive index silicones,” having arefractive index of at least about 1.46, preferably at least about 1.48,more preferably at least about 1.52, more preferably at least about1.55. The refractive index of the polysiloxane fluid will generally beless than about 1.70, typically less than about 1.60. In this context,polysiloxane “fluid” includes oils as well as gums.

[0125] The high refractive index polysiloxane fluid includes thoserepresented by general Formula (III) above, as well as cyclicpolysiloxanes such as those represented by Formula (VIII) below:

[0126] wherein R is as defined above, and n is a number from about 3 toabout 7, preferably from about 3 to about 5.

[0127] The high refractive index polysiloxane fluids contain an amountof aryl-containing R substituents sufficient to increase the refractiveindex to the desired level, which is described herein. Additionally, Rand n must be selected so that the material is non-volatile.

[0128] Aryl-containing substituents include those which containalicyclic and heterocyclic five and six member aryl rings and thosewhich contain fused five or six member rings. The aryl rings themselvescan be substituted or unsubstituted.

[0129] Generally, the high refractive index polysiloxane fluids willhave a degree of aryl-containing substituents of at least about 15%,preferably at least about 20%, more preferably at least about 25%, evenmore preferably at least about 35%, more preferably at least about 50%.Typically, the degree of aryl substitution will be less than about 90%,more generally less than about 85%, preferably from about 55% to about80%.

[0130] Preferred high refractive index polysiloxane fluids have acombination of phenyl or phenyl derivative substituents (more preferablyphenyl), with alkyl substituents, preferably C₁-C₄ alkyl (morepreferably methyl), hydroxy, or C₁-C₄ alkylamino (especially —R¹NHR²NH2wherein each R¹ and R² independently is a C₁-C₃ alkyl, alkenyl, and/oralkoxy).

[0131] When high refractive index silicones are used in the compositionsof the present invention, they are preferably used in solution with aspreading agent, such as a silicone resin or a surfactant, to reduce thesurface tension by a sufficient amount to enhance spreading and therebyenhance the glossiness (subsequent to drying) of hair treated with thecompositions.

[0132] Silicone fluids suitable for use in the compositions of thepresent invention are disclosed in U.S. Pat. No. 2,826,551, U.S. Pat.No. 3,964,500, U.S. Pat. No. 4,364,837, British Pat. No. 849,433, andSilicon Compounds, Petrarch Systems, Inc. (1984).

[0133] e. Silicone Resins

[0134] Silicone resins may be included in the silicone conditioningagent of the compositions of the present invention. These resins arehighly cross-linked polymeric siloxane systems. The cross-linking isintroduced through the incorporation of trifunctional andtetrafunctional silanes with monofunctional or difunctional, or both,silanes during manufacture of the silicone resin.

[0135] Silicone materials and silicone resins in particular, canconveniently be identified according to a shorthand nomenclature systemknown to those of ordinary skill in the art as “MDTQ” nomenclature.Under this system, the silicone is described according to presence ofvarious siloxane monomer units which make up the silicone. Briefly, thesymbol M denotes the monofunctional unit (CH₃)₃SiO_(0.5); D denotes thedifunctional unit (CH₃)₂SiO; T denotes the trifunctional unit(CH₃)SiO_(1.5); and Q denotes the quadra- or tetra-functional unit SiO₂.Primes of the unit symbols (e.g. M′, D′, T′, and Q′) denote substituentsother than methyl, and must be specifically defined for each occurrence.

[0136] Preferred silicone resins for use in the compositions of thepresent invention include, but are not limited to MQ, MT, MTQ, MDT andMDTQ resins. Methyl is a preferred silicone substituent. Especiallypreferred silicone resins are MQ resins, wherein the M:Q ratio is fromabout 0.5:1.0 to about 1.5:1.0 and the average molecular weight of thesilicone resin is from about 1000 to about 10,000.

[0137] The weight ratio of the non-volatile silicone fluid, havingrefractive index below 1.46, to the silicone resin component, when used,is preferably from about 4:1 to about 400:1, more preferably from about9:1 to about 200:1, more preferably from about 19:1 to about 100:1,particularly when the silicone fluid component is a polydimethylsiloxanefluid or a mixture of polydimethylsiloxane fluid andpolydimethylsiloxane gum as described herein. Insofar as the siliconeresin forms a part of the same phase in the compositions hereof as thesilicone fluid, i.e. the conditioning active, the sum of the fluid andresin should be included in determining the level of siliconeconditioning agent in the composition.

[0138] 2. Organic Conditioning Oils

[0139] The conditioning component of the compositions of the presentinvention may also comprise from about 0.05% to about 3%, preferablyfrom about 0.08% to about 1.5%, more preferably from about 0.1% to about1%, of at least one organic conditioning oil as the conditioning agent,either alone or in combination with other conditioning agents, such asthe silicones (described herein).

[0140] a. Hydrocarbon Oils

[0141] Suitable organic conditioning oils for use as conditioning agentsin the compositions of the present invention include, but are notlimited to, hydrocarbon oils having at least about 10 carbon atoms, suchas cyclic hydrocarbons, straight chain aliphatic hydrocarbons (saturatedor unsaturated), and branched chain aliphatic hydrocarbons (saturated orunsaturated), including polymers and mixtures thereof. Straight chainhydrocarbon oils preferably are from about C₁₂ to about C₁₉. Branchedchain hydrocarbon oils, including hydrocarbon polymers, typically willcontain more than 19 carbon atoms.

[0142] Specific non-limiting examples of these hydrocarbon oils includeparaffin oil, mineral oil, saturated and unsaturated dodecane, saturatedand unsaturated tridecane, saturated and unsaturated tetradecane,saturated and unsaturated pentadecane, saturated and unsaturatedhexadecane, polybutene, polydecene, and mixtures thereof. Branched-chainisomers of these compounds, as well as of higher chain lengthhydrocarbons, can also be used, examples of which include highlybranched, saturated or unsaturated, alkanes such as thepermethyl-substituted isomers, e.g., the permethyl-substituted isomersof hexadecane and eicosane, such as2,2,4,4,6,6,8,8-dimethyl-10-methylundecane and2,2,4,4,6,6-dimethyl-8-methylnonane, available from PermethylCorporation. Hydrocarbon polymers such as polybutene and polydecene. Apreferred hydrocarbon polymer is polybutene, such as the copolymer ofisobutylene and butene. A commercially available material of this typeis L-14 polybutene from Amoco Chemical Corporation. The concentration ofsuch hydrocarbon oils in the composition preferably range from about0.05% to about 20%, more preferably from about 0.08% to about 1.5%, andeven more preferably from about 0.1% to about 1%.

[0143] b. Polyolefins

[0144] Organic conditioning oils for use in the compositions of thepresent invention can also include liquid polyolefins, more preferablyliquid poly-α-olefins, more preferably hydrogenated liquidpoly-α-olefins. Polyolefins for use herein are prepared bypolymerization of C₄ to about C₁₄ olefenic monomers, preferably fromabout C₆ to about C₁₂.

[0145] Non-limiting examples of olefenic monomers for use in preparingthe polyolefin liquids herein include ethylene, propylene, 1-butene,1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene,branched chain isomers such as 4-methyl-1-pentene, and mixtures thereof.Also suitable for preparing the polyolefin liquids are olefin-containingrefinery feedstocks or effluents. Preferred hydrogenated α-olefinmonomers include, but are not limited to: 1-hexene to 1-hexadecenes,1-octene to 1-tetradecene, and mixtures thereof.

[0146] c. Fatty Esters

[0147] Other suitable organic conditioning oils for use as theconditioning agent in the compositions of the present invention include,but are not limited to, fatty esters having at least 10 carbon atoms.These fatty esters include esters with hydrocarbyl chains derived fromfatty acids or alcohols (e.g. mono-esters, polyhydric alcohol esters,and di- and tri-carboxylic acid esters). The hydrocarbyl radicals of thefatty esters hereof may include or have covalently bonded thereto othercompatible functionalities, such as amides and alkoxy moieties (e.g.,ethoxy or ether linkages, etc.).

[0148] Specific examples of preferred fatty esters include, but are notlimited to: isopropyl isostearate, hexyl laurate, isohexyl laurate,isohexyl palmitate, isopropyl palmitate, decyl oleate, isodecyl oleate,hexadecyl stearate, decyl stearate, isopropyl isostearate, dihexyldecyladipate, lauryl lactate, myristyl lactate, cetyl lactate, oleylstearate, oleyl oleate, oleyl myristate, lauryl acetate, cetylpropionate, and oleyl adipate.

[0149] Other fatty esters suitable for use in the compositions of thepresent invention are mono-carboxylic acid esters of the general formulaR′COOR, wherein R′ and R are alkyl or alkenyl radicals, and the sum ofcarbon atoms in R′ and R is at least 10, preferably at least 22.

[0150] Still other fatty esters suitable for use in the compositions ofthe present invention are di- and tri-alkyl and alkenyl esters ofcarboxylic acids, such as esters of C₄ to C₈ dicarboxylic acids (e.g. C₁to C₂₂ esters, preferably C₁ to C₆, of succinic acid, glutaric acid, andadipic acid). Specific non-limiting examples of di- and tri-alkyl andalkenyl esters of carboxylic acids include isocetyl stearyol stearate,diisopropyl adipate, and tristearyl citrate.

[0151] Other fatty esters suitable for use in the compositions of thepresent invention are those known as polyhydric alcohol esters. Suchpolyhydric alcohol esters include alkylene glycol esters, such asethylene glycol mono and di-fatty acid esters, diethylene glycol mono-and di-fatty acid esters, polyethylene glycol mono- and di-fatty acidesters, propylene glycol mono- and di-fatty acid esters, polypropyleneglycol monooleate, polypropylene glycol 2000 monostearate, ethoxylatedpropylene glycol monostearate, glyceryl mono- and di-fatty acid esters,polyglycerol poly-fatty acid esters, ethoxylated glyceryl monostearate,1,3-butylene glycol monostearate, 1,3-butylene glycol distearate,polyoxyethylene polyol fatty acid ester, sorbitan fatty acid esters, andpolyoxyethylene sorbitan fatty acid esters.

[0152] Still other fatty esters suitable for use in the compositions ofthe present invention are glycerides, including, but not limited to,mono-, di-, and tri-glycerides, preferably di- and tri-glycerides, morepreferably triglycerides. For use in the compositions described herein,the glycerides are preferably the mono-, di-, and tri-esters of glyceroland long chain carboxylic acids, such as C₁₀ to C₂₂ carboxylic acids. Avariety of these types of materials can be obtained from vegetable andanimal fats and oils, such as castor oil, safflower oil, cottonseed oil,corn oil, olive oil, cod liver oil, almond oil, avocado oil, palm oil,sesame oil, lanolin and soybean oil. Synthetic oils include, but are notlimited to, triolein and tristearin glyceryl dilaurate.

[0153] Other fatty esters suitable for use in the compositions of thepresent invention are water insoluble synthetic fatty esters. Somepreferred synthetic esters conform to the general Formula (IX):

[0154] wherein R¹ is a C₇ to C₉ alkyl, alkenyl, hydroxyalkyl orhydroxyalkenyl group, preferably a saturated alkyl group, morepreferably a saturated, linear, alkyl group; n is a positive integerhaving a value from 2 to 4, preferably 3; and Y is an alkyl, alkenyl,hydroxy or carboxy substituted alkyl or alkenyl, having from about 2 toabout 20 carbon atoms, preferably from about 3 to about 14 carbon atoms.Other preferred synthetic esters conform to the general Formula (X):

[0155] wherein R² is a C₈ to C₁₀ alkyl, alkenyl, hydroxyalkyl orhydroxyalkenyl group; preferably a saturated alkyl group, morepreferably a saturated, linear, alkyl group; n and Y are as definedabove in Formula (X).

[0156] Specific non-limiting examples of suitable synthetic fatty estersfor use in the compositions of the present invention include: P-43(C₈-C₁₀ triester of trimethylolpropane), MCP-684 (tetraester of 3,3diethanol-1,5 pentadiol), MCP 121 (C₈-C₁₀ diester of adipic acid), allof which are available from Mobil Chemical Company.

[0157] 3. Other Conditioning Agents

[0158] Also suitable for use in the compositions herein are theconditioning agents described by the Procter & Gamble Company in U.S.Pat. Nos. 5,674,478, and 5,750,122. Also suitable for use herein arethose conditioning agents described in U.S. Pat. No. 4,529,586(Clairol), U.S. Pat. No. 4,507,280 (Clairol), U.S. Pat. No. 4,663,158(Clairol), U.S. Pat. No. 4,197,865 (L'Oreal), U.S. Pat. No. 4,217,914(L'Oreal), U.S. Pat. No. 4,381,919 (L'Oreal), and U.S. Pat. No.4,422,853 (L'Oreal).

[0159] 4. Additional Components

[0160] The compositions of the present invention may further include avariety of additional useful components. Preferred additional componentsinclude those discussed below:

[0161] 1. Other Anti-Microbial Actives

[0162] The compositions of the present invention may further include oneor more anti-fungal or anti-microbial actives in addition to the metalpyrithione salt actives. Suitable anti-microbial actives include coaltar, sulfur, whitfield's ointment, castellani's paint, aluminumchloride, gentian violet, octopirox (piroctone olamine), ciclopiroxolamine, undecylenic acid and it's metal salts, potassium permanganate,selenium sulfide, sodium thiosulfate, propylene glycol, oil of bitterorange, urea preparations, griseofulvin, 8-Hydroxyquinoline ciloquinol,thiobendazole, thiocarbamates, haloprogin, polyenes, hydroxypyridone,morpholine, benzylamine, allylamines (such as terbinafine), tea treeoil, clove leaf oil, coriander, palmarosa, berberine, thyme red,cinnamon oil, cinnamic aldehyde, citronellic acid, hinokitol, ichthyolpale, Sensiva SC-50, Elestab HP-100, azelaic acid, lyticase,iodopropynyl butylcarbamate (IPBC), isothiazalinones such as octylisothiazalinone and azoles, and combinations thereof. Preferredanti-microbials include itraconazole, ketoconazole, selenium sulfide andcoal tar.

[0163] a. Azoles

[0164] Azole anti-microbials include imidazoles such as benzimidazole,benzothiazole, bifonazole, butaconazole nitrate, climbazole,clotrimazole, croconazole, eberconazole, econazole, elubiol,fenticonazole, fluconazole, flutimazole, isoconazole, ketoconazole,lanoconazole, metronidazole, miconazole, neticonazole, omoconazole,oxiconazole nitrate, sertaconazole, sulconazole nitrate, tioconazole,thiazole, and triazoles such as terconazole and itraconazole, andcombinations thereof. When present in the composition, the azoleanti-microbial active is included in an amount from about 0.01% to about5%, preferably from about 0.1% to about 3%, and more preferably fromabout 0.3% to about 2%, by weight of the composition. Especiallypreferred herein is ketoconazole.

[0165] b. Selenium Sulfide

[0166] Selenium sulfide is a particulate anti-dandruff agent suitablefor use in the anti-microbial compositions of the present invention,effective concentrations of which range from about 0.1% to about 4%, byweight of the composition, preferably from about 0.3% to about 2.5%,more preferably from about 0.5% to about 1.5%. Selenium sulfide isgenerally regarded as a compound having one mole of selenium and twomoles of sulfur, although it may also be a cyclic structure thatconforms to the general formula Se_(x)S_(y), wherein x+y=8. Averageparticle diameters for the selenium sulfide are typically less than 15μm, as measured by forward laser light scattering device (e.g. Malvern3600 instrument), preferably less than 10 μm. Selenium sulfide compoundsare described, for example, in U.S. Pat. No. 2,694,668; U.S. Pat. No.3,152,046; U.S. Pat. No. 4,089,945; and U.S. Pat. No. 4,885,107.

[0167] c. Sulfur

[0168] Sulfur may also be used as a particulateanti-microbial/anti-dandruff agent in the anti-microbial compositions ofthe present invention. Effective concentrations of the particulatesulfur are typically from about 1% to about 4%, by weight of thecomposition, preferably from about 2% to about 4%.

[0169] d. Keratolytic Agents

[0170] The present invention may further comprise one or morekeratolytic agents such as Salicylic Acid.

[0171] Additional anti-microbial actives of the present invention mayinclude extracts of melaleuca (tea tree) and charcoal. The presentinvention may also comprise combinations of anti-microbial actives. Suchcombinations may include octopirox and zinc pyrithione combinations,pine tar and sulfur combinations, salicylic acid and zinc pyrithionecombinations, octopirox and climbasole combinations, and salicylic acidand octopirox combinations, and mixtures thereof.

[0172] 2. Hair loss prevention and Hair Growth Agents

[0173] The present invention may further comprise materials useful forhair loss prevention and hair growth stimulants or agents. Examples ofsuch agents are Anti-Androgens such as Propecia, Dutasteride, RU5884;Anti-Inflammatories such as Glucocortisoids, Macrolides, Macrolides;Anti-Microbials such as Zinc pyrithione, Ketoconazole, Seleniumsulfiled, Acne Treatments; Immunosuppressives such as FK-506,Cyclosporin; vasodilators such as minoxidil, Aminexil® and combinationsthereof.

[0174] 3. Sensates

[0175] The present invention may further comprise topical sensatematerials such as terpenes, vanilloids, alkyl amides, natural extractsand combinations thereof. Terpenes can include menthol and derivativessuch as menthyl lactate, ethyl menthane carboxamide, andmenthoyxypropanediol. Other terpenes can include camphor, eucalyptol,carvone, thymol and combinations thereof. Vanilloids can includecapsaicin, zingerone, eugenol, and vanillyl butyl ether. Alkyl amidescan include spilanthol, hydroxy alpha-sanschool, pellitorine andcombinations thereof. Natural extracts can include peppermint oil,eucalyptol, rosemary oil, ginger oil, clove oil, capsicum, jambuextract, cinnamon oil, laricyl and combinations thereof. Additionaltopical sensate materials can include methyl salicylate, anethole,benzocaine, lidocane, phenol, benzyl nicotinate, nicotinic acid,cinnamic aldehyde, cinnamyl alcohol, piperine, and combinations thereof.

[0176] 4. Humectant

[0177] The compositions of the present invention may contain ahumectant. The humectants herein are selected from the group consistingof polyhydric alcohols, water soluble alkoxylated nonionic polymers, andmixtures thereof. The humectants, when used herein, are preferably usedat levels of from about 0.1% to about 20%, more preferably from about0.5% to about 5%.

[0178] Polyhydric alcohols useful herein include glycerin, sorbitol,propylene glycol, butylene glycol, hexylene glycol, ethoxylated glucose,1, 2-hexane diol, hexanetriol, dipropylene glycol, erythritol,trehalose, diglycerin, xylitol, maltitol, maltose, glucose, fructose,sodium chondroitin sulfate, sodium hyaluronate, sodium adenosinephosphate, sodium lactate, pyrrolidone carbonate, glucosamine,cyclodextrin, and mixtures thereof.

[0179] Water soluble alkoxylated nonionic polymers useful herein includepolyethylene glycols and polypropylene glycols having a molecular weightof up to about 1000 such as those with CTFA names PEG-200, PEG-400,PEG-600, PEG-1000, and mixtures thereof.

[0180] 5. Suspending Agent

[0181] The compositions of the present invention may further comprise asuspending agent at concentrations effective for suspendingwater-insoluble material in dispersed form in the compositions or formodifying the viscosity of the composition. Such concentrations rangefrom about 0.1% to about 10%, preferably from about 0.3% to about 5.0%.

[0182] Suspending agents useful herein include polymeric suspendingagents such as anionic polymers and nonionic polymers. Useful herein arevinyl polymers such as cross linked acrylic acid polymers with the CTFAname Carbomer, cellulose derivatives and modified cellulose polymerssuch as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose,hydroxypropyl methyl cellulose, nitro cellulose, sodium cellulosesulfate, sodium carboxymethyl cellulose, crystalline cellulose,cellulose powder, polyvinylpyrrolidone, polyvinyl alcohol, guar gum,hydroxypropyl guar gum, xanthan gum, arabia gum, tragacanth, galactan,carob gum, guar gum, karaya gum, carragheenin, pectin, agar, quince seed(Cydonia oblonga Mill), starch (rice, corn, potato, wheat), algaecolloids (algae extract), microbiological polymers such as dextran,succinoglucan, pulleran, starch-based polymers such as carboxymethylstarch, methylhydroxypropyl starch, alginic acid-based polymers such assodium alginate, alginic acid propylene glycol esters, acrylate polymerssuch as sodium polyacrylate, polyethylacrylate, polyacrylamide,polyethyleneimine, and inorganic water soluble material such asbentonite, aluminum magnesium silicate, laponite, hectonite, andanhydrous silicic acid.

[0183] Commercially available viscosity modifiers highly useful hereininclude Carbomers with tradenames Carbopol 934, Carbopol 940, Carbopol950, Carbopol 980, and Carbopol 981, all available from B. F. GoodrichCompany, acrylates/steareth-20 methacrylate copolymer with tradenameACRYSOL 22 available from Rohm and Hass, nonoxynyl hydroxyethylcellulosewith tradename AMERCELL POLYMER HM-1500 available from Amerchol,methylcellulose with tradename BENECEL, hydroxyethyl cellulose withtradename NATROSOL, hydroxypropyl cellulose with tradename KLUCEL, cetylhydroxyethyl cellulose with tradename POLYSURF 67, all supplied byHercules, ethylene oxide and/or propylene oxide based polymers withtradenames CARBOWAX PEGs, POLYOX WASRs, and UCON FLUIDS, all supplied byAmerchol.

[0184] Other optional suspending agents include crystalline suspendingagents which can be categorized as acyl derivatives, long chain amineoxides, and mixtures thereof. These suspending agents are described inU.S. Pat. No. 4,741,855. These preferred suspending agents includeethylene glycol esters of fatty acids preferably having from about 16 toabout 22 carbon atoms. More preferred are the ethylene glycol stearates,both mono and distearate, but particularly the distearate containingless than about 7% of the mono stearate. Other suitable suspendingagents include alkanol amides of fatty acids, preferably having fromabout 16 to about 22 carbon atoms, more preferably about 16 to 18 carbonatoms, preferred examples of which include stearic monoethanolamide,stearic diethanolamide, stearic monoisopropanolamide and stearicmonoethanolamide stearate. Other long chain acyl derivatives includelong chain esters of long chain fatty acids (e.g., stearyl stearate,cetyl palmitate, etc.); long chain esters of long chain alkanol amides(e.g., stearamide diethanolamide distearate, stearamide monoethanolamidestearate); and glyceryl esters (e.g., glyceryl distearate,trihydroxystearin, tribehenin) a commercial example of which is Thixin Ravailable from Rheox, Inc. Long chain acyl derivatives, ethylene glycolesters of long chain carboxylic acids, long chain amine oxides, andalkanol amides of long chain carboxylic acids in addition to thepreferred materials listed above may be used as suspending agents.

[0185] Other long chain acyl derivatives suitable for use as suspendingagents include N,N-dihydrocarbyl amido benzoic acid and soluble saltsthereof (e.g., Na, K), particularly N,N-di(hydrogenated) C.sub.16,C.sub.18 and tallow amido benzoic acid species of this family, which arecommercially available from Stepan Company (Northfield, Ill., USA).

[0186] Examples of suitable long chain amine oxides for use assuspending agents include alkyl dimethyl amine oxides, e.g., stearyldimethyl amine oxide.

[0187] Other suitable suspending agents include primary amines having afatty alkyl moiety having at least about 16 carbon atoms, examples ofwhich include palmitamine or stearamine, and secondary amines having twofatty alkyl moieties each having at least about 12 carbon atoms,examples of which include dipalmitoylamine or di(hydrogenatedtallow)amine. Still other suitable suspending agents includedi(hydrogenated tallow)phthalic acid amide, and crosslinked maleicanhydride-methyl vinyl ether copolymer.

[0188] 6. Other Optional Components

[0189] The compositions of the present invention may contain alsovitamins and amino acids such as: water soluble vitamins such as vitaminB1, B2, B6, B12, C, pantothenic acid, pantothenyl ethyl ether,panthenol, biotin, and their derivatives, water soluble amino acids suchas asparagine, alanin, indole, glutamic acid and their salts, waterinsoluble vitamins such as vitamin A, D, E, and their derivatives, waterinsoluble amino acids such as tyrosine, tryptamine, and their salts.

[0190] The compositions of the present invention may also containpigment materials such as inorganic, nitroso, monoazo, disazo,carotenoid, triphenyl methane, triaryl methane, xanthene, quinoline,oxazine, azine, anthraquinone, indigoid, thionindigoid, quinacridone,phthalocianine, botanical, natural colors, including: water solublecomponents such as those having C. I. Names. The compositions of thepresent invention may also contain antimicrobial agents which are usefulas cosmetic biocides and antidandruff agents including: water solublecomponents such as piroctone olamine, water insoluble components such as3,4,4′-trichlorocarbanilide (triclocarban), triclosan and zincpyrithione.

[0191] The compositions of the present invention may also containchelating agents.

[0192] H. Coordinating Compound Having a Log Zn Bindinq Constant

[0193] In an embodiment of the present invention, the compositionfurther comprises a coordinating compound with a Log Zn binding constantin a range sufficient to maintain zinc bioavailability. Preferably, sucha coordinating compound has a Log Zn binding constant less than about 6,preferably less than about 5, more preferable less than about 4, andgreater than about −0.5. Preferably such a coordinating compound is anorganic acid, strong mineral acid, or coordinating species. Preferredexamples of such coordinating compounds include the following(respective Log Zn Binding Constant indicated in parenthesis): EDTA(16.5), EDDS (13.5), EDDA (11.1), NTA (10.7), Xylenol Orange (10.3),Cysteine (9.1), Cystine (6.7), Aspartic Acid (Aspartate) (5.9), Glycine(5.0), Citric Acid (Citrate) (4.8), Glutamic Acid (4.5), Methionine(4.4), Arginine (4.2), Carbonic Acid (Carbonate) (3.9), Ornithine (3.8),Tatronic Acid (Tartrate) (3.2), Malic Acid (Malate) (2.9), Malonic Acid(Malonate) (2.9), Tartaric Acid (Tartrate) (2.7), Adipic Acid (Adipate)(2.6),Phosphoric Acid (Phosphate) (2.4), Phthalic Acid (Phthalate)(2.2), Glycolic Acid (Glycolate) (2.0), Lactic Acid (Lactate) (1.9),Succinic Acid (Succinate) (1.8), Acetic Acid (Acetate) (1.0), SulfuricAcid (Sulfate) (0.9), Boric Acid (Borate) (0.9), Formic Acid (Formate)(0.6), Chloride (˜0.3).

[0194] I. pH

[0195] In embodiments of the present invention, the pH may be in a rangeof from about 6.5 to about 12, preferably from about 6.7 to about 9,more preferably from about 6.8 to about 8.2, even more preferably fromabout 7.0 to about 8.0. In preferred embodiments, the pH of the presentinvention may be greater than about 6.5, more preferably greater thanabout 6.8, and still more preferably, greater than about 7.

[0196] In an embodiment of the present invention, the graph in FIG. 1demonstrates the relationship between pH and percent (%) soluble zinc.An acid level study is demonstrated wherein solubility and pH aremeasured in a composition. As the pH goes below 7.5, the % soluble zincmeasured in a composition begins to rise. In the data below, citric acidappears to dissolve more zinc in the composition when compared tohydrochloric acid (HCl), on a weight basis.

[0197] J. Classification of Zinc-Containing Materials According to theirZinc Availability

[0198] Zinc-containing materials (ZCMs) differ with respect to howstrongly the zinc ion (Zn ²⁺) is held by counterions in the crystallattice. The benefits discussed herein depend upon having availableZn²⁺. To determine which ZCMs provide sufficient labile Zn ²⁺ and thosethat do not, a test was developed using a metallochromic dye whichchanges color upon coordinating Zn²⁺. The response is a binary visualassessment of whether or not the color changes indicating zinc-binding.If the color changes, the ZCM is classified as having available Zn²⁺whereas if it does not change, the ZCM is not useful for this invention.

[0199] The method is based on the commercial metallochromic dye zincon.Zincon changes from an orange color to blue upon binding zinc andprovides the basis for detecting available Zn²⁺:

[0200] The specific procedure involves making a stock solution of zinconin ethanol (˜50 mg/10 ml ethanol). The ZCM is then added to water (˜30mg/10 ml water) and agitated (pH range should be 7-11). Three to fourdrops of zincon solution are then added to the ZCM in water, agitatedand a visual assessment of color change made.

[0201] Using this methodology, the following ZCM are examples of thosethat have available zinc: zinc chloride, zinc sulfate, zinc citrate,zinc oxide, zinc acetate, zinc stearate, zinc lactate, zinc salicylate,zinc arginine, zinc histadine, zinc hexaborate, zinc hydroxide, zincoxalate, zinc monoglycerolate and the like. Examples of ZCM not havingavailable Zn²⁺ are zinc EDTA, zinc sulfide, zinc phytate and othermaterials with very tightly bound zinc.

[0202] In an embodiment of the present invention, the compositioncomprises from 5% to 50% of a surfactant; a zinc containing materialwherein zinc availability is measured by a zinc ion reacting with ametallochromic dye zincon to give a dye color change from orange toblue. In another embodiment of the present invention, the compositioncomprises from 5% to 50% of a surfactant; a zinc containing materialwherein zinc availability is measured by a zinc ion reacting with ametallochromic dye zincon to give a dye color change from orange toblue; and a zinc ionophore.

[0203] K. Method for Assessment of Zinc Lability in Zinc-ContainingProducts

[0204] Zinc lability is a measure of the chemical availability of zincion. Soluble zinc salts that do not complex with other species insolution have a relative zinc lability, by definition, of 100%. The useof partially soluble forms of zinc salts and/or incorporation in amatrix with potential complexants generally lowers the zinc labilitysubstantially below the defined 100% maximum.

[0205] Zinc lability is assessed by combining a diluted zinc-containingsolution or dispersion with the metallochromic dye xylenol orange (XO)and measurement of the degree of color change under specifiedconditions. The magnitude of color formation is proportional to thelevel of labile zinc. The procedure developed has been optimized foraqueous surfactant formulations but may be adapted to other physicalproduct forms as well.

[0206] A spectrophotometer is used to quantify the color change at 572nm, the wavelength of optimum color change for XO. The spectrophotometeris set to zero absorbance at 572 nm utilizing a product control as closein composition to the test product except excluding the potentiallylabile form of zinc. The control and test products are then treatedidentically as follows. A 50 μl product sample is dispensed into a jarand 95 ml of deaerated, distilled water are added and stirred. 5 mL of a23 mg/mL xylenol orange stock solution at pH 5.0 is pipetted into thesample jar; this is considered time 0. The pH is then adjusted to5.50±0.01 using dilute HCl or NaOH. After 10.0 minutes, a portion of thesample is filtered (0.45μ) and the absorbance measured at 572 nm. Themeasured absorbance is then compared to a separately measured control todetermine the relative zinc lability (zero TO 100%). The 100% labilitycontrol is prepared in a matrix similar to the test products bututilizing a soluble zinc material (such as zinc sulfate) incorporated atan equivalent level on a zinc basis. The absorbance of the 100% labilitycontrol is measured as above for the test materials. The relative zinclability is preferably greater than about 15%, more preferably greaterthan about 20%, and even more preferably greater than about 25%.

[0207] Using this methodology, the below examples demonstrate a material(hydrozincite) that has intrinsically high lability in an anionicsurfactant system compared to one (ZnO) with low intrinsic lability. Theexamples further demonstrate that the low lability of ZnO can beimproved substantially by incorporating a protective material such assodium bicarbonate, a source of carbonate anions and mixtures thereof:Relative Zinc Lability (%) Simple Surfactant Simple Surfactant System¹Plus System¹ Alone Sodium Bicarbonate² Zinc Oxide 1.5 33.2 Hydrozincite37.0

[0208] L. Methods of Manufacture for Shampoo Compositions

[0209] The compositions of the present invention may be prepared by anyknown or otherwise effective technique, suitable for providing ananti-microbial composition provided that the resulting compositionprovides the excellent anti-microbial benefits described herein. Methodsfor preparing the anti-dandruff and conditioning shampoo embodiments ofthe present invention include conventional formulation and mixingtechniques. A method such as that described in U.S. Pat. No. 5,837,661,could be employed, wherein the anti-microbial agent of the presentinvention would typically be added in the same step as the siliconepremix is added in the U.S. Pat. No. 5,837,661 description.

[0210] M. Methods of Use

[0211] The compositions of the present invention may be used in directapplication to the skin or in a conventional manner for cleansing skinand hair and controlling microbial infection (including fungal, viral,or bacterial infections) on the skin or scalp. The compositions hereinare useful for cleansing the hair and scalp, and other areas of the bodysuch as underarm, feet, and groin areas and for any other area of skinin need of treatment. The present invention may be used for treating orcleansing of the skin or hair of animals as well. An effective amount ofthe composition, typically from about 1 g to about 50 g, preferably fromabout 1 g to about 20 g of the composition, for cleansing hair, skin orother area of the body, is topically applied to the hair, skin or otherarea that has preferably been wetted, generally with water, and thenrinsed off. Application to the hair typically includes working theshampoo composition through the hair.

[0212] A preferred method for providing anti-microbial (especiallyanti-dandruff) efficacy with a shampoo embodiment comprises the stepsof: (a) wetting the hair with water, (b) applying an effective amount ofthe anti-microbial shampoo composition to the hair, and (c) rinsing theanti-microbial shampoo composition from the hair using water. Thesesteps may be repeated as many times as desired to achieve the cleansing,conditioning, and anti-microbial/anti-dandruff benefits sought.

[0213] It is also contemplated that when the anti-microbial activeemployed is zinc pyrithione, and/or if other optional hair growthregulating agents are employed, the anti-microbial compositions of thepresent invention, may, provide for the regulation of growth of thehair. The method of regularly using such shampoo compositions comprisesrepeating steps a, b, and c (above).

[0214] A further embodiment of the present invention comprises a methodcomprising the steps of (a) wetting the hair with water, (b) applying aneffective amount of a shampoo composition comprising a zinc ionophore,(c) rinsing the shampoo compositions from the hair using water; (d)applying an effective amount of a conditioner composition comprising azinc containing material according to the present invention; (e) rinsingthe conditioner composition from the hair using water. In a furtherembodiment, this method could be conducted wherein steps d and b arereversed. In a further embodiment, steps b and d can vary and be ashampoo, hair lotions, hair sprays, hair tonics, conditioningtreatments, gels, mousses and dressings, and the like. A preferredembodiment of the above mentioned method includes a shampoo compositioncomprising zinc pyrithione and a conditioner composition comprising zincoxide.

[0215] A further embodiment of the present invention comprises a methodof treating athlete's foot comprising the use of the compositionaccording to the present invention, a method of treating microbialinfections comprising the use of composition as described herein, methodof improving the appearance of a scalp comprising the use of thecomposition according present invention, a method of treating fungalinfections comprising the use of the composition according to thepresent invention, a method of treating dandruff comprising the use ofthe composition of the present invention, a method of treating diaperdermatitis and candidiasis comprising the use of the compositions of thepresent invention as described herein, a method of treating tineacapitis comprising the use of the composition according to the presentinvention, a method of treating yeast infections comprising the use ofthe composition according to the present invention, a method of treatingonychomycosis comprising the use of the composition according to thepresent invention.

N. EXAMPLES

[0216] The following examples further describe and demonstrate thepreferred embodiments within the scope of the present invention. Theexamples are given solely for the purpose of illustration, and are notto be construed as limitations of the present invention since manyvariations thereof are possible without departing from its scope.

[0217] The composition of the invention can be made by mixing one ormore selected metal ion sources and one or more metal salts ofpyrithione in an appropriate media or carrier, or by adding theindividual components separately to the skin or hair cleansingcompositions. Useful carriers are discussed more fully above.

[0218] 1. Topical Compositions

[0219] All exemplified compositions can be prepared by conventionalformulation and mixing techniques. Component amounts are listed asweight percents and exclude minor materials such as diluents, filler,and so forth. The listed formulations, therefore, comprise the listedcomponents and any minor materials associated with such components. Asused herein, “minors” refers to those optional components such aspreservatives, viscosity modifiers, pH modifiers, fragrances, foamboosters, and the like. As is apparent to one of ordinary skill in theart, the selection of these minors will vary depending on the physicaland chemical characteristics of the particular ingredients selected tomake the present invention as described herein. Other modifications canbe undertaken by the skilled artisan without departing from the spiritand scope of this invention. These exemplified embodiments of theanti-microbial shampoo, anti-microbial cleansing compositions,anti-microbial cleansing/facial compositions of the present inventionprovide excellent anti-microbial efficacy.

Antimicrobial Shampoo—Examples 1-54

[0220] A suitable method for preparing the anti-microbial shampoocompositions described in Examples 1-54 (below) follows:

[0221] About one-third to all of the sodium laureth sulfate (added as 25wt % solution) and acid are added to a jacketed mix tank and heated toabout 60° C. to about 80° C. with slow agitation to form a surfactantsolution. The pH of this solution is about 7.5. Sodium benzoate,Cocoamide MEA and fatty alcohols, (where applicable), are added to thetank and allowed to disperse. Ethylene glycol distearate (“EGDS”) isadded to the mixing vessel and allowed to melt (where applicable). Afterthe EGDS is melted and dispersed, Kathon CG is added to the surfactantsolution. The resulting mixture is cooled to about 25° C. to about 40°C. and collected in a finishing tank. As a result of this cooling step,the EGDS crystallizes to form a crystalline network in the product(where applicable). The remainder of the sodium laureth sulfate andother components, including the silicone and anti-microbial agent(s),are added to the finishing tank with agitation to ensure a homogeneousmixture. Polymers (cationic or nonionic) are dispersed in water or oilsas an about 0.1% to about 10% dispersion and/or solution and then addedto the final mix. ZnO or Zinc Hydroxy carbonate (“ZHC”) can be added toa premix of surfactants or water with or without the aid of a dispersingagent via conventional powder incorporation and mixing techniques intothe final mix. Adjustment of ZnO particle size can be affected byvarious conventional mixing techniques obvious to one skilled in theart. Once all components have been added, additional viscosity modifiersmay be added, as needed, to the mixture to adjust product viscosity tothe extent desired.

Shampoo Compositions—Examples 1-10

[0222] Example Components Example 1 Example 2 Example 3 Example 4Example 5 Example 6 Example 7 Example 8 Example 9 10 Sodium LaurethSulfate 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00Sodium Lauryl Sulfate 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00Cocamidopropyl Betaine Sodium Cocoisethionate EGDS 1.50 1.50 1.50 1.501.50 1.50 1.50 1.50 1.50 1.50 CMEA 0.800 0.800 0.800 0.800 0.800 0.8000.800 0.800 0.800 1.600 Cetyl Alcohol 0.600 0.600 0.600 0.600 0.6000.600 0.600 0.600 0.600 0.600 Guar Hydroxy Propyl 0.500 0.500 0.5000.500 0.500 0.500 0.500 0.500 0.500 0.500 Trimonium Chloride (1) GuarHydroxy Propyl Trimonium Chloride (2) Guar Hydroxy Propyl TrimoniumChloride (3) Polyquaterium-10 (4) Polyquaterium-10 (5) PEG-7M (6)PEG-14M (7) PEG-45M (8) Dimethicone (9) 0.85 0.85 0.85 0.85 0.85 0.850.85 0.85 0.85 0.85 Dimethicone (10) ZPT (11) 1.00 2.00 2.00 1.00 1.001.00 1.00 1.00 1.00 1.00 Zinc Oxide 1.20 1.20 0.60 0.60 0.30 1.20 1.201.20 1.20 1.20 Zinc Hydroxy Carbonate Sodium Bicarbonate 0.20 0.20 0.200.20 0.20 0.10 0.05 0.25 0.20 Hydrochloric Acid 0.78 0.78 0.78 0.78 0.780.53 0.40 0.91 0.28 0.78 Magnesium Sulfate 0.28 0.28 0.28 0.28 0.28 0.280.28 0.28 0.28 0.28 Sodium Chloride 0.800 0.800 0.800 0.800 0.800 0.8000.800 0.800 0.800 0.800 Sodium Xylenesulfonate Perfume 0.750 0.750 0.7500.750 0.750 0.750 0.750 0.750 0.750 0.750 Sodium Benzoate 0.250 0.2500.250 0.250 0.250 0.250 0.250 0.250 0.250 0.250 Kathon 0.0008 0.00080.0008 0.0008 0.0008 0.0008 0.0008 0.0008 0.0008 0.0008 Benzyl Alcohol0.0225 0.0225 0.0225 0.0225 0.0225 0.0225 0.0225 0.0225 0.0225 0.0225Water Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. % Maximum XO63.2% 38.9% 38.5% 63.9% 23.5% 88.8% Lability % Soluble Zinc 0.024 0.0172.55 × 10⁻³ 5.01 × 10⁻³ 0.011

Shampoo Compositions—Examples 11-20

[0223] Example Example Example Example Example Example Example ExampleExample Components 11 12 13 14 15 16 17 18 19 Example 20 Sodium LaurethSulfate 10.00 10.00 10.00 10.00 10.00 12.50 10.00 10.00 10.00 10.00Sodium Lauryl Sulfate 6.00 6.00 6.00 6.00 6.00 1.50 6.00 6.00 6.00 6.00Cocamidopropyl Betaine 2.00 2.70 Sodium Cocoisethionate EGDS 1.50 1.501.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 CMEA 1.600 0.800 0.800 1.6000.800 0.800 0.800 0.800 0.800 0.800 Cetyl Alcohol 0.600 0.600 0.6000.600 0.600 0.600 0.600 0.600 0.600 0.600 Guar Hydroxy Propyl 0.5000.500 0.500 0.500 0.500 0.500 0.500 0.500 Trimonium Chloride (1) GuarHydroxy Propyl 0.500 Trimonium Chloride (2) Guar Hydroxy Propyl 0.500Trimonium Chloride (3) Polyquaterium-10 (4) Polyquaterium-10 (5) PEG-7M(6) 0.200 0.200 PEG-14M (7) PEG-45M (8) 0.200 Dimethicone (9) 0.85 0.850.85 0.85 0.85 0.85 0.85 0.85 0.85 0.85 Dimethicone (10) ZPT (11) 1.001.00 1.00 1.00 1.00 1.00 1.00 Zinc Oxide 1.20 1.20 1.20 1.20 1.20 1.201.20 1.20 0.60 0.30 Zinc Hydroxy Carbonate Sodium Bicarbonate 0.20 0.200.20 0.20 0.20 0.20 0.20 Hydrochloric Acid 0.78 0.78 0.78 0.78 0.78 0.780.78 0.28 0.28 0.28 Magnesium Sulfate 0.28 0.28 0.28 0.28 0.28 0.28 0.280.28 0.28 0.28 Sodium Chloride 0.800 0.800 0.800 0.800 0.800 0.800 0.8000.800 0.800 0.800 Sodium Xylenesulfonate Perfume 0.750 0.750 0.750 0.7500.750 0.750 0.750 0.750 0.750 0.750 Sodium Benzoate 0.250 0.250 0.2500.250 0.250 0.250 0.250 0.250 0.250 0.250 Kathon 0.0008 0.0008 0.00080.0008 0.0008 0.0008 0.0008 0.0008 0.0008 0.0008 Benzyl Alcohol 0.02250.0225 0.0225 0.0225 0.0225 0.0225 0.0225 0.0225 0.0225 0.0225 WaterQ.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. % Maximum XO Lability59.8% 58.2% 72.9% 71.7% 67.2% % Soluble Zinc

Shampoo Compositions—Examples 21-30

[0224] Example Example Example Example Example Example Example ExampleExample Components 21 22 23 24 25 26 27 28 29 Example 30 Sodium LaurethSulfate 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00Sodium Lauryl Sulfate 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00Cocamidopropyl Betaine Sodium Cocoisethionate EGDS 1.50 1.50 1.50 1.501.50 1.50 1.50 1.50 1.50 1.50 CMEA 0.800 0.800 0.800 0.800 0.800 0.8000.800 0.800 0.800 0.800 Cetyl Alcohol 0.600 0.600 0.600 0.600 0.6000.600 0.600 0.600 0.600 0.600 Guar Hydroxy Propyl 0.500 0.400 0.2500.500 0.500 0.500 0.500 0.500 0.500 Trimonium Chloride (1) Guar HydroxyPropyl Trimonium Chloride (2) Guar Hydroxy Propyl Trimonium Chloride (3)Polyquaterium-10 (4) Polyquaterium-10 (5) 0.500 0.500 0.100 PEG-7M (6)0.100 0.100 PEG-14M (7) PEG-45M (8) Dimethicone (9) 0.85 1.40 0.85 0.850.85 0.85 1.35 1.00 0.85 0.85 Dimethicone (10) ZPT (11) 1.00 1.00 1.001.00 1.00 0.50 1.00 1.00 2.00 2.00 Zinc Oxide 1.20 1.20 1.20 1.20 ZincHydroxy Carbonate 1.61 1.61 1.61 1.61 1.61 0.80 Sodium Bicarbonate 0.200.20 0.20 0.20 Hydrochloric Acid 0.78 0.78 0.78 0.78 0.42 0.42 0.42 0.420.42 0.42 Magnesium Sulfate 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.280.28 Sodium Chloride 0.800 0.800 0.800 0.800 0.800 0.800 0.800 0.8000.800 0.800 Sodium Xylenesulfonate Perfume 0.750 0.750 0.750 0.750 0.7500.750 0.750 0.750 0.750 0.750 Sodium Benzoate 0.250 0.250 0.250 0.2500.250 0.250 0.250 0.250 0.250 0.250 Kathon 0.0008 0.0008 0.0008 0.00080.0008 0.0008 0.0008 0.0008 0.0008 0.0008 Benzyl Alcohol 0.0225 0.02250.0225 0.0225 0.0225 0.0225 0.0225 0.0225 0.0225 0.0225 Water Q.S. Q.S.Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. % Maximum XO Lability 74.0% %Soluble Zinc 0.022

Shampoo Compositions—Examples 31-40

[0225] Example Example Example Example Example Example Example ExampleExample Components 31 32 33 34 35 36 37 38 39 Example 40 Sodium LaurethSulfate 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00Sodium Lauryl Sulfate 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00Cocamidopropyl Betaine Sodium Cocoisethionate EGDS 1.50 1.50 1.50 1.501.50 1.50 1.50 1.50 1.50 1.50 CMEA 0.800 0.800 1.600 0.800 0.800 1.6000.800 0.800 0.800 0.800 Cetyl Alcohol 0.600 0.600 0.600 0.600 0.6000.600 0.600 0.600 0.600 0.600 Guar Hydroxy Propyl 0.500 0.500 0.5000.500 0.500 0.500 0.500 Trimonium Chloride (1) Guar Hydroxy Propyl 0.500Trimonium Chloride (2) Guar Hydroxy Propyl 0.500 0.500 TrimoniumChloride (3) Polyquaterium-10 (4) Polyquaterium-10 (5) PEG-7M (6) 0.2000.100 PEG-14M (7) 0.200 PEG-45M (8) 0.200 Dimethicone (9) 0.85 0.85 0.850.85 0.85 0.85 0.85 0.85 0.85 Dimethicone (10) 1.00 ZPT (11) 2.00 1.001.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 Zinc Oxide Zinc HydroxyCarbonate 0.40 1.61 1.61 1.61 1.61 1.61 1.61 1.61 1.61 1.61 SodiumBicarbonate Hydrochloric Acid 0.42 0.42 0.42 0.42 0.42 0.42 0.42 0.420.42 0.42 Magnesium Sulfate 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.280.28 Sodium Chloride 0.800 0.800 0.800 0.800 0.800 0.800 0.800 0.8000.800 0.800 Sodium Xylenesulfonate Perfume 0.750 0.750 0.750 0.750 0.7500.750 0.750 0.750 0.750 0.750 Sodium Beuzoate 0.250 0.250 0.250 0.2500.250 0.250 0.250 0.250 0.250 0.250 Kathon 0.0008 0.0008 0.0008 0.00080.0008 0.0008 0.0008 0.0008 0.0008 0.0008 Benzyl Alcohol 0.0225 0.02250.0225 0.0225 0.0225 0.0225 0.0225 0.0225 0.0225 0.0225 Water Q.S. Q.S.Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. % Maximum XO Lability 65.6%76.2% % Soluble Zinc

Shampoo Compositions—Examples 41-50

[0226] Example Example Example Example Example Example Example ExampleExample Components 41 42 43 44 45 46 47 48 49 Example 50 Sodium LaurethSulfate 10.00 12.50 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00Sodium Lauryl Sulfate 6.00 1.50 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00Cocamidopropyl Betaine 2.00 2.70 Sodium Cocoisethionate 2.00 EGDS 1.501.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 CMEA 0.800 0.800 0.8001.600 1.600 0.800 0.800 0.800 0.800 0.800 Cetyl Alcohol 0.600 0.6000.600 0.600 0.600 0.600 0.600 0.600 0.600 0.600 Guar Hydroxy Propyl0.500 0.500 0.500 0.500 Trimonium Chloride (1) Guar Hydroxy PropylTrimonium Chloride (2) Guar Hydroxy Propyl Trimonium Chloride (3)Polyquaterium-10 (4) 0.500 0.500 Polyquaterium-10 (5) 0.500 0.500 0.5000.250 PEG-7M (6) 0.200 0.100 0.100 PEG-14M (7) PEG-45M (8) Dimethicone(9) 0.85 0.85 0.85 0.85 1.40 1.40 1.40 1.40 0.85 0.85 Dimethicone (10)ZPT (11) 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 Zinc OxideZinc Hydroxy Carbonate 1.61 1.61 1.61 1.61 1.61 1.61 1.61 1.61 1.61 1.61Sodium Bicarbonate Hydrochloric Acid 0.42 0.42 0.42 0.42 0.42 0.42 0.420.42 0.42 0.42 Magnesium Sulfate 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.280.28 0.28 Sodium Chloride 0.800 0.800 0.800 0.800 0.800 0.800 0.8000.800 0.800 0.800 Sodium Xylenesulfonate Perfume 0.750 0.750 0.750 0.7500.750 0.750 0.750 0.750 0.750 0.750 Sodium Beazoate 0.250 0.250 0.2500.250 0.250 0.250 0.250 0.250 0.250 0.250 Kathon 0.0008 0.0008 0.00080.0008 0.0008 0.0008 0.0008 0.0008 0.0008 0.0008 Benzyl Alcohol 0.02250.0225 0.0225 0.0225 0.0225 0.0225 0.0225 0.0225 0.0225 0.0225 WaterQ.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. % Maximum XO Lability66.7% 66.9% % Soluble Zinc

Shampoo Compositions—Examples 51-54

[0227] Example Example Components Example 51 Example 52 Example 53 54A54B Sodium Laureth Sulfate 10.00 10.00 10.00 10.00 10.00 Sodium LaurylSulfate 6.00 6.00 6.00 6.00 6.00 Cocamidopropyl Betaine SodiumCocoisethionate EGDS 1.50 1.50 1.50 1.50 1.50 CMEA 0.800 0.800 0.8000.800 0.800 Cetyl Alcohol 0.600 0.600 0.600 0.600 0.600 Guar HydroxyPropyl Trimonium 0.400 0.500 Chloride (1) Guar Hydroxy Propyl Trimonium0.500 0.500 0.500 Chloride (2) Guar Hydroxy Propyl Trimonium Chloride(3) Polyquaterium-10 (4) Polyquaterium-10 (5) 0.100 PEG-7M (6) 0.100PEG-14M (7) PEG-45M (8) Dimethicone (9) 0.85 0.85 0.85 0.85 0.85Dimethicone (10) ZPT (11) 1.00 Zinc Oxide Zinc Hydroxy Carbonate 1.611.61 0.80 0.40 1.61 Sodium Bicarbonate Fumaric Acid 0.53 HydrochloricAcid 0.42 0.42 0.42 0.42 Magnesium Sulfate 0.28 0.28 0.28 0.28 0.28Sodium Chloride 0.800 0.800 0.800 0.800 0.800 Sodium XylenesulfonatePerfume 0.750 0.750 0.750 0.750 0.750 Sodium Benzoate 0.250 0.250 0.2500.250 0.250 Kathon 0.0008 0.0008 0.0008 0.0008 0.0008 Benzyl Alcohol0.0225 0.0225 0.0225 0.0225 0.0225 Water Q.S. Q.S. Q.S. Q.S. Q.S. %Maximum XO Lability % Soluble Zinc

Cleansing Compositions—Examples 55-61

[0228] A suitable method for preparing the anti-microbial cleansingcompositions described in Examples 55-61 (below) follows:

[0229] Components 1-3, 9, and 10 are mixed with heating to 190F.Components 4, 12, 15 and 17 are mixed at room temperature in a separatepot. After the first mixture has reached 190F, it is added to the secondmixture. After this mixture has cooled below 140 F, components 13 (& 5)is added. In a separate vessel at 160 F, the petrolatum and ZnO or ZHCare mixed. When the aqueous phase has cooled below 110 F, thepetrolatum/ZnO or ZHC blend is added and agitated until smooth. ZnO orZHC can also be added to a premix of surfactants or water with orwithout the aid of a dispersing agent via conventional powderincorporation and mixing techniques into the cooled mixture. Adjustmentof ZnO particle size can be affected by various conventional mixingtechniques obvious to one skilled in the art. Finally the perfume isadded. Components Example 55 Example 56 Example 57 Example 58 Example 59Example 60 Example 61 1 Sodium Lauryl Sulfate 4.000 4.000 4.000 4.0004.000 4.000 4.000 2 Sodium Laureth Sulfate 3.000 3.000 3.000 3.000 3.0003.000 3.000 3 Sodium 4.000 4.000 4.000 4.000 4.000 4.000 4.000Laruroamphoacetate 4 Sodium Lauroyl 2.000 2.000 2.000 2.000 2.000 2.0002.000 Sarcosinate 5 Zinc Pyrithione (1) 1.000 6 Zinc Oxide treated 2.0006.000 6.000 with silicone (2) 7 Zinc Oxide 2.000 5.000 8 Zinc HydroxyCarbonate 2.000 4.000 9 Lauric Acid 1.000 1.000 1.000 1.000 1.000 1.0001.000 10 Trihydroxystearin 0.650 0.650 0.650 0.650 0.650 0.650 0.650 11Citric Acid as needed as needed as needed as needed as needed as neededas needed 12 Sodium Benzoate 0.250 0.250 0.250 0.250 0.250 0.250 0.25013 Glydant 0.120 0.120 0.120 0.120 0.120 0.120 0.120 14 Perfume 0.7500.750 0.750 0.750 0.750 0.750 0.750 15 Polyquaterium-10 (3) 0.750 0.7500.750 0.750 0.750 0.750 0.750 16 Petrolatum 15.000 15.000 15.000 15.00015.000 15.000 15.000 17 Water Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S.

Cleansing/Facial Compositions—Examples 62-75

[0230] A suitable method for preparing the anti-microbialcleansing/facial compositions described in Examples 62-75 are known tothose skilled in the art, and may be prepared by any known or otherwiseeffective technique, suitable for providing an anti-microbialcleansing/facial composition provided that the resulting compositionprovides the excellent anti-microbial benefits described herein. Methodsfor preparing the anti-microbial cleansing/facial compositionsembodiments of the present invention include conventional formulationand mixing techniques. A method such as that described in U.S. Pat. No.5,665,364, could be employed. Components Example 62 Example 63 Example64 Example 65 Example 66 Example 67 Example 68 Cetyl Betaine 6.667 6.6676.667 6.667 6.667 6.667 6.667 PPG-15 Stearyl Ether 4.000 4.000 4.0004.000 4.000 4.000 4.000 Sodium Lauryl Sulfate 3.571 3.571 3.571 3.5713.571 3.571 3.571 Distearyldimonium Chloride Glycerin 3.000 3.000 3.0003.000 3.000 3.000 3.000 Stearyl Alcohol 2.880 2.880 2.880 2.880 2.8802.880 2.880 Distearyldimonium Chloride 1.500 1.500 1.500 1.500 1.5001.500 1.500 Oxidized Polyethylene 1.000 1.000 1.000 1.000 1.000 1.0001.000 Zinc Pyrithione (1) 1.000 Zinc Oxide 1.200 0.600 0.300 1.200 ZincHydroxy Carbonate 1.610 0.800 0.400 Cetyl Alcohol 0.800 0.800 0.8000.800 0.800 0.800 0.800 Steareth-21 0.500 0.500 0.500 0.500 0.500 0.5000.500 Behenyl Alcohol 0.320 0.320 0.320 0.320 0.320 0.320 0.320 PPG-300.250 0.250 0.250 0.250 0.250 0.250 0.250 Steareth-2 0.250 0.250 0.2500.250 0.250 0.250 0.250 Perfume 0.200 0.200 0.200 0.200 0.200 0.2000.200 Citric Acid As Needed As Needed As Needed As Needed As Needed AsNeeded As Needed Sodium Citrate As Needed As Needed As Needed As NeededAs Needed As Needed As Needed Water Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S.Components Example 69 Example 70 Example 71 Example 72 Example 73Example 74 Example 75 Sodium Laureth Sulfate 8.000 8.000 8.000 8.0008.000 8.000 8.000 Disodium Cocamphodiacetate 7.000 7.000 7.000 7.0007.000 7.000 7.000 PEG-80 Glyceryl Cocoate 3.500 3.500 3.500 3.500 3.5003.500 3.500 Sodium Chloride 2.170 2.170 2.170 2.170 2.170 2.170 2.170Glycol Distearate 2.000 2.000 2.000 2.000 2.000 2.000 2.000 ZincPyrithione (1) 1.000 Zinc Oxide 1.200 0.600 0.300 1.200 Zinc HydroxyCarbonate 1.610 0.800 0.400 Dimethicone 0.900 0.900 0.900 0.900 0.9000.900 0.900 Sodium Trideceth-7 0.502 0.502 0.502 0.502 0.502 0.502 0.502Carboxylate Perfume 0.320 0.320 0.320 0.320 0.320 0.320 0.320 CitricAcid As needed As needed As needed As needed As needed As needed Asneeded Quaternium-15 0.150 0.150 0.150 0.150 0.150 0.150 0.150Polyquaterium-10 0.150 0.150 0.150 0.150 0.150 0.150 0.150 PEG-30Glyceryl Cocoate As Needed As Needed As Needed As Needed As Needed AsNeeded As Needed Water Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S.

[0231] 10. Other Ingredients

[0232] The present invention may, in some embodiments, further compriseadditional optional components known or otherwise effective for use inhair care or personal care products. The concentration of such optionalingredients generally ranges from zero to about 25%, more typically fromabout 0.05% to about 20%, even more typically from about 0.1% to about15%, by weight of the composition. Such optional components should alsobe physically and chemically compatible with the essential componentsdescribed herein, and should not otherwise unduly impair productstability, aesthetics or performance.

[0233] Non-limiting examples of optional components for use in thepresent invention include anti-static agents, foam boosters,anti-dandruff agents in addition to the anti-dandruff agents describedabove, viscosity adjusting agents and thickeners, suspension materials(e.g. EGDS, thixins), pH adjusting agents (e.g. sodium citrate, citricacid, succinic acid, sodium succinate, sodium maleate, sodium glycolate,malic acid, glycolic acid, hydrochloric acid, sulfuric acid, sodiumbicarbonate, sodium hydroxide, and sodium carbonate), preservatives(e.g. DMDM hydantoin), anti-microbial agents (e.g. triclosan ortriclocarbon), dyes, organic solvents or diluents, pearlescent aids,perfumes, fatty alcohols, proteins, skin active agents, sunscreens,vitamins (such as retinoids including retinyl propionate, vitamin E suchas tocopherol acetate, panthenol, and vitamin B3 compounds includingniacinamide), emulsifiers, volatile carriers, select stability actives,styling polymers, organic styling polymers, silicone-grafted stylingpolymers, cationic spreading agents, pediculocides, foam boosters,viscosity modifiers and thickeners, polyalkylene glycols andcombinations thereof.

[0234] Optional anti-static agents such as water-insoluble cationicsurfactants may be used, typically in concentrations ranging from about0.1% to about 5%, by weight of the composition. Such anti-static agentsshould not unduly interfere with the in-use performance and end-benefitsof the anti-microbial composition; particularly, the anti-static agentshould not interfere with the anionic surfactant. A specificnon-limiting example of a suitable anti-static agents is tricetyl methylammonium chloride.

[0235] Optional foam boosters for use in the present invention describedherein include fatty ester (e.g. C₈-C₂₂) mono- and di (C₁-C₅, especiallyC₁-C₃) alkanol amides. Specific non-limiting examples of such foamboosters include coconut monoethanolamide, coconut diethanolamide, andmixtures thereof.

[0236] Optional viscosity modifiers and thickeners may be used,typically in amounts effective for the anti-microbial compositions ofthe present invention to generally have an overall viscosity from about1,000 csk to about 20,000 csk, preferably from about 3,000 csk to about10,000 csk. Specific non-limiting examples of such viscosity modifiersand thickeners include: sodium chloride, sodium sulfate, and mixturesthereof.

[0237] O. Other Preferred Embodiments

[0238] Other preferred embodiments of the present invention include thefollowing:

[0239] An embodiment of the present invention relates to a compositioncomprising 5% to 50% of a surfactant, an effective amount of a zinccontaining material and from 40% to 95% water. Preferably the zinccontaining material in having an aqueous solubility within thecomposition of less than about 25% by weight at 25° C. Preferably thezinc containing material for such a composition is an inorganicmaterial, natural zinc containing material, ore, mineral, organic salt,polymeric salt, physically adsorbed form material, or mixtures thereof.Preferably the inorganic material in such a composition is a zincaluminate, zinc carbonate, zinc oxide, calamine, zinc phosphate, zincselenide, zinc sulfide, zinc silicate, zinc silicofluoride, zinc borate,or zinc hydroxide, zinc hydroxy sulfate, or mixtures thereof. Preferablythe surfactant in such a composition is anionic, cationic, nonionic,amphoteric or zwitterionic surfactants, or mixtures thereof; morepreferably a mixture of an anionic surfactant and a zwitterionicsurfactant, or anionic surfactant and amphoteric surfactant.

[0240] Another embodiment of the present invention relates to acomposition comprising from about 5% to about 50% of a surfactant; fromabout 0.001% to about 10% of zinc oxide; and a ZIM; wherein the pH ofthe composition is greater than about 7; and wherein the ZIM is a zincionophore, hydrophobic zinc material, or mixtures thereof. Anotherembodiment of the present invention relates to a composition comprisingfrom about 5% to about 50% of a surfactant; from about 0.001% to about10% of zinc hydroxycarbonate, and a ZIM; wherein the pH of thecomposition is greater than about 7; and wherein the ZIM is a zincionophore, hydrophobic zinc material, or mixtures thereof. Preferablythe ZIM in such a composition is a polyvalent metal salt of pyrithione,dithiocarbamate, heterocyclic amine, nonsteriodal anti-inflammatorycompound, naturally occurring material having zinc ionophoric behavior,derivative of a naturally occurring material having zinc ionophoricbehavior, bio-molecule, pepetide, sulfur-based compound, transportenhancer, or mixtures thereof; more preferably a pyrithione or a zincsalt of pyrithione; more preferably still, zinc pyrithione. The pH ofsuch a composition is preferably from about 7.0 to 9. Preferably such acomposition comprises a compound having a having a Log zinc bindingconstant of less than about 6; preferably such a compound is an organicacid, strong mineral acid, zinc coordinating species, or mixturesthereof; more preferably the compound is sodium bicarbonate. Preferablythe surfactant in such a composition is anionic, cationic, nonionic,amphoteric, zwitterionic, or mixtures thereof. Preferably the zinccontaining material is present in such a composition in an amount of0.1% to about 3% by weight of the composition. Preferably such acomposition further comprises a conditioning agent. Preferably such acomposition further comprises a cationic deposition polymer.

[0241] In a preferred embodiment, the zinc containing material has aaqueous solubility within a composition of less than about 25% by weightat 25° C.

[0242] In another embodiment of the present invention, the compositionembodiment may be employed to treat a variety of conditions, including:athlete's foot, microbial infections, improving the appearance of ascalp, treating fungal infections, treating dandruff, treating diaperdermatitis and candidiasis, treating tinea capitis, treating yeastinfections, treating onychomycosis. Preferably such conditions aretreated by applying a composition of the present invention to theaffected area.

[0243] While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

What is claimed is:
 1. A composition comprising: a. an effective amountof a zinc containing material having an aqueous solubility within thecomposition of less than about 25% by weight at 25° C.; b. from about 5%to about 50% of a surfactant; and c. from about 40% to about 95% water;wherein the pH of the composition is greater than about
 7. 2. Thecomposition according to claim 1 wherein the zinc containing materialhas a relative zinc lability of greater than about 15%.
 3. Thecomposition of claim 1, wherein composition comprises from about 0.001%to about 10% of the zinc containing material.
 4. The compositionaccording to claim 1 wherein the zinc containing material is selectedfrom the group consisting of inorganic materials, natural zinccontaining materials, ores, minerals, organic salts, polymeric salts, orphysically adsorbed form material and mixtures thereof.
 5. Thecomposition according to claim 4 wherein the inorganic material isselected from the group consisting of zinc aluminate, zinc carbonate,zinc oxide, calamine, zinc phosphate, zinc selenide, zinc sulfide, zincsilicates, zinc silicofluoride, zinc borate, or zinc hydroxide and zinchydroxy sulfate, zinc-containing layered material and mixtures thereof6. The composition according to claim 5 wherein the inorganic materialis zinc oxide.
 7. The composition according to claim 6 wherein thecomposition further comprises a component selected from the groupconsisting of sodium bicarbonate, sources of carbonate anions andmixtures thereof.
 8. The composition according to claim 7 wherein thecomposition further comprises a compound having a Log zinc bindingconstant of less than about
 6. 9. The composition according to claim 8wherein the Log zinc binding constant is less than about
 5. 10. Thecomposition according to claim 9 wherein the Log zinc binding constantis less than about
 4. 11. The composition according to claim 5 whereinthe zinc-containing layered material is selected from the groupconsisting of basic zinc carbonate hydroxide, zinc copper carbonate,copper zinc carbonate hydroxide, phyllosilicate containing zinc ions,layered double hydroxide, hydroxy double salts and mixtures thereof. 12.The composition according to claim 11 wherein the zinc-containinglayered material is selected from the group consisting of zinchydroxycarbonate, hydrozincite, basic zinc carbonate and mixturesthereof.
 13. The composition according to claim 12 wherein thezinc-containing layered material is hydrozincite or basic zinccarbonate.
 14. The composition according to claim 13 wherein thezinc-containing layered material is selected from the group consistingof materials formed synthetically, materials formed in situ in acomposition, or materials formed during the production process.
 15. Thecomposition according to claim 1 wherein the zinc containing materialhas a relative zinc lability of greater than about 20%.
 16. Thecomposition according to claim 1 wherein the zinc containing materialhas a relative zinc lability of greater than about 25%.
 17. Thecomposition according to claim 1 wherein the surfactant is selected fromthe group consisting of anionic, cationic, nonionic, amphoteric orzwitterionic surfactants and mixtures thereof.
 18. The compositionaccording to claim 17 wherein the surfactant is a mixture of an anionicsurfactant and a zwitterionic or amphoteric surfactant.
 19. Thecomposition according to claim 18 wherein the surfactant is an anionicsurfactant.
 20. A composition comprising: a. an effective amount of azinc containing material having an aqueous solubility within thecomposition of less than about 25% by weight at 25° C.; b. from about 5%to about 50% of a surfactant; and c. from about 0.1% to about 5% of azinc ionophoric material; d. from about 40% to about 95% water; andwherein the pH of the composition is greater than about
 7. 21. Acomposition according to claim 20 wherein the zinc containing materialhas a relative lability of greater than about 15%.
 22. The compositionaccording to claim 20 wherein the zinc ionophoric material is selectedfrom the group consisting of polyvalent metal salts of pyrithiones,dithiocarbamates, heterocyclic amines, nonsteriodal anti-inflammatorycompounds, naturally occurring materials having zinc ionophoricbehavior, and derivatives thereof, bio-molecules and peptides,sulfur-based compounds, transport enhancers and mixtures thereof.
 23. Acomposition according to claim 20 wherein the zinc ionophoric materialis pyrithione or a zinc salt of pyrithione.
 24. A composition accordingto claim 23 wherein the zinc ionophoric material is zinc pyrithione. 25.The composition of claim 20 wherein composition comprises from about0.001% to about 10% of the zinc containing material.
 26. The compositionaccording to claim 25 wherein the zinc containing material is selectedfrom the group consisting of inorganic materials, natural zinccontaining materials, ores, minerals, organic salts, polymeric salts, orphysically adsorbed form material and mixtures thereof.
 27. Thecomposition according to claim 26 wherein the inorganic material isselected from the group consisting of zinc aluminate, zinc carbonate,zinc oxide, calamine, zinc phosphate, zinc selenide, zinc sulfide, zincsilicates, zinc silicofluoride, zinc borate, or zinc hydroxide and zinchydroxy sulfate, zinc-containing layered material and mixtures thereof.28. The composition according to claim 27 wherein the inorganic materialis zinc oxide.
 29. The composition according to claim 28 wherein thecomposition further comprises a component selected from the groupconsisting of sodium bicarbonate, sources of carbonate anions andmixtures thereof.
 30. The composition according to claim 29 wherein thecomposition further comprises a compound having a Log zinc bindingconstant of less than about
 6. 31. The composition according to claim 30wherein the Log zinc binding constant is less than about
 5. 32. Thecomposition according to claim 31 wherein the Log zinc binding constantis less than about
 4. 33. The composition according to claim 27 whereinthe zinc-containing layered material is selected from the groupconsisting of basic zinc carbonate hydroxide, zinc copper carbonate,copper zinc carbonate hydroxide, phyllosilicate containing zinc ions,layered double hydroxide, hydroxy double salts and mixtures thereof. 34.The composition according to claim 27 wherein the zinc-containinglayered material is selected from the group consisting of zinchydroxycarbonate, hydrozincite, basic zinc carbonate and mixturesthereof.
 35. The composition according to claim 34 wherein thezinc-containing layered material is hydrozincite or basic zinccarbonate.
 36. The composition according to claim 20 wherein the zinccontaining material has a relative zinc lability of greater than about20%.
 37. The composition according to claim 20 wherein the zinccontaining material has a relative zinc lability of greater than about25%.
 38. A composition comprising: a. an effective amount of a zinccontaining material having an aqueous solubility within the compositionof less than about 25% by weight at 25° C.; b. from about 5% to about50% of a surfactant; c. from about 0.1% to about 10% of a suspendingagent; d. from about 40% to about 95% water; and wherein the pH of thecomposition is greater than about
 7. 39. A composition according toclaim 38 wherein the suspending agent is selected from the groupconsisting of crystalline suspending agents, polymeric suspending agentsor mixtures thereof.
 40. A composition according to claim 39 wherein thesuspending agent is a crystalline suspending agent.
 41. The compositionaccording to claims 1, 20 or 38 wherein the composition furthercomprises a conditioning agent.
 42. The composition according to claims1, 20 or 38 wherein the composition further comprises a cationicdeposition polymer.
 43. The composition according to claims 1, 20 or 38wherein the zinc containing material has a particle size of from about100 nm to about 30 μm.
 44. A method of treating microbial infectionscomprising the use of the composition of claims 1, 20 or
 38. 45. Amethod of treating fungal infections comprising the use of thecomposition of claims 1, 20 or
 38. 46. A method of treating dandruffcomprising the use of the composition of claims 1, 20 or 38.